CN114538508B - Zirconium dioxide powder and preparation method thereof - Google Patents
Zirconium dioxide powder and preparation method thereof Download PDFInfo
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- CN114538508B CN114538508B CN202210192764.XA CN202210192764A CN114538508B CN 114538508 B CN114538508 B CN 114538508B CN 202210192764 A CN202210192764 A CN 202210192764A CN 114538508 B CN114538508 B CN 114538508B
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- 239000000843 powder Substances 0.000 title claims abstract description 111
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 45
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 39
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 37
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 26
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 4
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 12
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 8
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 5
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 5
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 5
- LWHHUEHWVBVASY-UHFFFAOYSA-N erbium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LWHHUEHWVBVASY-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 15
- 238000000227 grinding Methods 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- -1 zirconium alkoxide Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910018626 Al(OH) Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000011351 dental ceramic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WLVFWCBILFUUJZ-UHFFFAOYSA-N gold(3+) oxygen(2-) zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4].[Au+3] WLVFWCBILFUUJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010939 rose gold Substances 0.000 description 1
- 229910001112 rose gold Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
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- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of zirconium dioxide powder, which comprises the following steps: mixing the first raw material and the second raw material, and rubbing and drying to obtain precursor powder; and calcining the precursor powder to obtain the zirconium dioxide powder. Wherein the first raw material is a high-purity zirconium organic alkoxide solution or the first raw material comprises a high-purity zirconium organic alkoxide solution and a metal salt solution; the second raw material is a solid auxiliary agent which can be decomposed under the condition of heating or friction. The high-purity zirconium organic alkoxide comprises more than one of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide or zirconium ethoxide. The solid auxiliary agent comprises more than one of ammonium bicarbonate, ammonium carbonate or ammonium carbamate. The zirconium dioxide powder prepared by the preparation method is also provided. The preparation method of the zirconium dioxide powder provided by the invention has the advantages of simple steps, loose preparation conditions, uniform particle size, small particles, few impurities and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetallic materials, and particularly relates to zirconium dioxide powder and a preparation method thereof.
Background
Zirconium dioxide (ZrO 2) powder has been an important dental ceramic, refractory and catalytic material because of its melting point up to 2700 ℃, high electrical resistivity, low thermal conductivity (1000 ℃, 2.09W/(m·k)), high expansion coefficient, and excellent mechanical properties, and its readily available raw materials, low toxicity, stable chemical properties.
At present, main preparation methods of the superfine zirconium dioxide powder include a coprecipitation method, a hydrothermal method, a chemical vapor deposition method, a solid phase method, an alkoxide hydrolysis method and a sol-gel method. The zirconium dioxide powder prepared by the preparation method has various defects, such as colloid is easy to form in the preparation process by the traditional coprecipitation method, so that the powder is difficult to filter and serious hard agglomeration occurs; in the preparation process of the hydrothermal method, the operation is complicated, the requirements on the temperature and the pressure of the preparation are severe, and the filtering step is needed finally; the chemical vapor deposition method is not easy to be industrially popularized in the field of biological ceramics due to high preparation cost; the powder product prepared by the traditional inorganic salt solid phase method has more impurities and is easy to cause uneven powder particles; the reaction speed of the alcoholysis is high, the control is difficult, the obtained high-purity particles are almost primary particles, but the preparation process is relatively complex, and a large amount of solvent is needed; the sol-gel method has the problems of difficult control of reaction conditions, difficult industrial mass production and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide zirconium dioxide powder and a preparation method thereof, thereby solving the problems of more impurities, uneven powder particles, harsh reaction conditions, complex preparation process and the like in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of zirconium dioxide powder comprises the following steps:
mixing the first raw material and the second raw material, and rubbing and drying to obtain precursor powder; calcining the precursor powder to obtain zirconium dioxide powder;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or the first raw material comprises a high-purity zirconium organic alkoxide solution and a metal salt solution; the second raw material is a solid auxiliary agent which can be decomposed under the condition of heating or friction.
The technical scheme is further improved as follows:
the high-purity zirconium organic alkoxide comprises one or more of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide or zirconium ethoxide.
The solid auxiliary agent comprises one or more of ammonium bicarbonate, ammonium carbonate or ammonium carbamate.
The mass ratio of the second raw material to the first raw material is 0.05-6:1.
When the first feedstock comprises a high purity zirconium organic alkoxide solution and a metal salt solution, the molar ratio of the metal salt to the zirconium source in the high purity zirconium organic alkoxide solution is from 0.001 to 0.5:1.
the purity of the high-purity zirconium organic alkoxide solution is more than analytical purity.
The friction includes grinding or ball milling; the friction time is 10-720min.
The calcination temperature of the precursor powder ranges from 500 ℃ to 1500 ℃ and the calcination time ranges from 0.5h to 6h.
The metal salt is strong acid weak alkali salt, and comprises one or more of yttrium chloride hexahydrate, erbium nitrate pentahydrate, aluminum nitrate nonahydrate, chromium nitrate nonahydrate, aluminum trichloride hexahydrate and cobalt acetate tetrahydrate.
The invention also provides zirconium dioxide powder prepared by the preparation method.
According to the technical scheme of the invention, the zirconium alkoxide which is easy to purify is taken as a zirconium source, the water in the air and the decomposition product of the solid auxiliary agent are taken as an H2O source to hydrolyze the zirconium alkoxide, the reaction process involves three phases of solid, liquid and gas, the process is simple, the reaction condition is loose, the energy consumption is small, the method is suitable for industrial production, the filtration steps for preparing the powder by a coprecipitation method and a hydrothermal method are reduced, the hard agglomeration phenomenon of the powder is effectively prevented, and the prepared powder product has high particle uniformity, small particle size and high purity.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing zirconium dioxide powder according to an embodiment of the present invention.
FIG. 2 is an XRD pattern of zirconium dioxide powder prepared in example 1 of the present invention.
FIG. 3 is a particle size distribution diagram of zirconium dioxide powder prepared in example 1 of the present invention.
Fig. 4 is an XRD pattern of the zirconium dioxide powder prepared in example 2 of the present invention.
FIG. 5 is a nitrogen adsorption isotherm of zirconium dioxide powder prepared in example 2 of the present invention.
FIG. 6 is an XRD pattern of zirconium dioxide powder prepared in example 3 of the present invention.
Fig. 7 is an XRD pattern of the zirconium dioxide powder prepared in example 4 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As shown in fig. 1, the preparation method of the zirconium dioxide powder in the embodiment of the invention comprises the following steps:
s1, adding a proper amount of second raw materials into the first raw materials to obtain a mixture of the two;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or the first raw material comprises a high-purity zirconium organic alkoxide solution and a metal salt solution; the second raw material is a solid auxiliary agent which can be decomposed under the condition of heating or friction;
the high-purity zirconium organic alkoxide comprises one or more of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide or zirconium ethoxide; the purity of the high-purity zirconium organic alkoxide solution is more than analytical purity;
the solid auxiliary agent comprises one or more of ammonium bicarbonate, ammonium carbonate or ammonium carbamate;
the mass ratio of the second raw material to the first raw material is 0.05-6:1;
when the first feedstock comprises a high purity zirconium organic alkoxide solution and a metal salt solution, the molar ratio of the metal salt to the zirconium source in the high purity zirconium organic alkoxide solution is from 0.001 to 0.5:1, a step of; the metal salt is strong acid weak alkali salt, and comprises one or more of yttrium chloride hexahydrate, erbium nitrate pentahydrate, aluminum nitrate nonahydrate, chromium nitrate nonahydrate, aluminum trichloride hexahydrate and cobalt acetate tetrahydrate.
S2, grinding or ball milling the mixture obtained in the step S1 in air for 10-720min, wherein the grinding or ball milling time can be 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min, 300min, 360min and the like; obtaining loose precursor powder after drying treatment; the temperature range of the drying treatment is 60-80 ℃.
The drying process can decompose the residual solid auxiliary agent.
The grinding or ball milling time of the mixture in the air does not directly influence the crystal phase of the zirconium dioxide powder, and the longer the friction time is, the more favorable the precursor powder with smaller particle size is formed, so that the particle size is more uniform.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, so as to obtain the zirconium dioxide powder. The calcination temperature ranges from 500 ℃ to 1500 ℃, for example, the calcination temperature may be 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, etc.; the calcination time is 0.5h-6h, for example, the calcination time may be 1h, 2h, 3h, 4h, 5h, etc.
The calcination temperature can directly influence the crystalline phase and the porous structure of the powder, and different calcination temperatures and calcination times can be designed according to specific requirements.
Example 1 the preparation method of the zirconium dioxide powder of this example is consistent with the above steps, and the specific implementation data are as follows:
s1, selecting a zirconium n-butoxide solution as a first raw material and selecting ammonium carbonate as a second raw material;
firstly, placing 10g of a commercial solution of zirconium n-butoxide with the mass fraction of 80% in an agate mortar, wherein the purity of the zirconium n-butoxide is analytically pure, and then adding 10g of ammonium carbonate solid into the agate mortar, wherein the purity of the ammonium carbonate is also analytically pure, so as to obtain the mixture.
S2, grinding the mixture obtained in the step S1 in air for 30min, wherein zirconium n-butoxide continuously absorbs moisture in the air and ammonium carbonate is decomposed ((NH) 4 ) 2 CO 3 →2NH 3 ↑+H 2 O↑+CO 2 ∈) resulting in continuous hydrolysis (Zr (OR) 4 +4H 2 O→Zr(OH) 4 ∈+4HOR ∈); at the same time, the solvent in the zirconium n-butoxide solution gradually volatilizes, and the mixture gradually changes into loose white powder from paste. And (3) placing the white powder in an oven at 80 ℃ for drying treatment to decompose residual ammonium carbonate, so as to obtain loose precursor powder.
S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1150 ℃ and the calcination time is 2 hours, so as to obtain white zirconium dioxide powder (Zr (OH) 4 →ZrO 2 +2H 2 O)。
FIG. 2 shows the XRD pattern of the zirconium dioxide powder obtained in example 1, in which the diffraction peaks are sharp and which is similar to those of monoclinic zirconium dioxide (ZrO 2 ) Standard card (JCPDS: 88-2390) shows that the product prepared by the method of this example is high crystallinity monoclinic zirconia.
FIG. 3 is a particle size distribution chart of the zirconium dioxide powder obtained in example 1, and it is clear from FIG. 3 that the particle size distribution range of the powder is narrow, showing that the particle size uniformity is high and the median diameter D 50 1.189 mu m, belonging to superfine powder.
Example 2 the preparation method of the zirconium dioxide powder of this example is substantially the same as that of example 1, and the specific implementation data are as follows:
s1, selecting a zirconium n-butoxide solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 15.2g of a commercial solution of zirconium n-butoxide with the mass fraction of 80% is put into a ball milling tank, the purity of the zirconium n-butoxide is analytically pure, and then 16.4g of ammonium bicarbonate solid is added into the ball milling tank, and the purity of the ammonium bicarbonate is also analytically pure, so that the mixture is obtained.
S2, ball milling the mixture obtained in the step S1 in air for 720min, wherein in the ball milling process, zirconium n-butoxide continuously absorbs water in the air and water generated by decomposition of ammonium bicarbonate, so that the zirconium n-butoxide is continuously hydrolyzed; at the same time, the solvent in the zirconium n-butoxide solution gradually volatilizes, and the mixture gradually changes into loose white powder from paste. And (3) placing the white powder in an oven at 80 ℃ for drying treatment, so that residual ammonium bicarbonate is decomposed, and loose precursor powder is obtained.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 600 ℃, and the calcination time is 2 hours, so that white zirconium dioxide powder is obtained.
Fig. 4 is an XRD pattern of the zirconium dioxide powder prepared in example 2, and as can be seen from fig. 4, the white ultrafine powder prepared is zirconium dioxide powder. In order to study that the powder has a porous structure, a nitrogen adsorption test was performed on the powder, and the specific surface area of the zirconium dioxide powder was 33.1m 2 Per g, pore volume of 0.0874cm 3 And/g, average pore diameter of 10.7nm. FIG. 5 shows the nitrogen adsorption isotherm of the powder, and the hysteresis loop of FIG. 5 can indicate that the powder is a mesoporous material.
Example 3 the preparation method of the zirconium dioxide powder of this example is substantially the same as example 1, and the specific implementation data are as follows:
s1, selecting a zirconium n-butoxide solution and a yttrium chloride hexahydrate solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.63g of yttrium chloride hexahydrate is dissolved in 3g of ethanol to obtain a metal salt solution, then the metal salt solution and 10.63g of 80% zirconium n-butoxide commercial solution are placed in a mortar for uniform mixing, the purity of the zirconium n-butoxide is analytically pure, and then 10.63g of ammonium bicarbonate solid (the purpose of the rapid addition is to enable the ammonium bicarbonate to be in contact with zirconium alkoxide as soon as possible) is rapidly added into the mortar, and the purity of the ammonium bicarbonate is analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in air for 10min, and slowly changing the mixture from paste to loose white powder. And (3) placing the white powder in a 60 ℃ oven for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1200 ℃, and the calcination time is 2 hours, so that yttrium-doped white zirconium dioxide powder is obtained.
Fig. 6 shows XRD patterns of the zirconium dioxide powder prepared in example 3, and the decrease in diffraction intensity of the powder is shown in fig. 6, indicating that the crystallinity of the powder is decreased after doping with yttrium metal, and that the yttrium doping is successful.
Example 4 the preparation method of the zirconium dioxide powder of this example is substantially the same as that of example 3, and the specific implementation data are as follows:
s1, selecting a zirconium n-butoxide solution and an erbium nitrate pentahydrate solution as a first raw material, and selecting ammonium bicarbonate and ammonium carbonate as a second raw material;
dissolving 0.4g of erbium nitrate pentahydrate in 3g of methanol to obtain a metal salt solution, then placing the metal salt solution and 10g of 80% zirconium n-butoxide solution in a mortar for uniform mixing, wherein the purity of zirconium n-propoxide is analytically pure, and then rapidly adding 5.4g of ammonium bicarbonate and 5g of ammonium carbonate solid into the mortar, wherein the purities of the ammonium bicarbonate and the ammonium carbonate are analytically pure, so as to obtain the mixture.
S2, grinding the mixture obtained in the step S1 in air for 20min, and then placing the mixture in a 70 ℃ oven for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1150 ℃, and the calcination time is 2 hours, so that the erbium-doped rose gold zirconium dioxide powder is obtained.
Fig. 7 is an XRD pattern of the zirconium dioxide powder prepared in example 4, and it is understood from fig. 7 that the powder has a zirconium dioxide crystal phase.
Example 5 the preparation method of the zirconium dioxide powder of this example is substantially the same as example 4, and the specific implementation data are as follows:
s1, selecting a zirconium n-propoxide solution and an aluminum nitrate nonahydrate solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 3.91g of aluminum nitrate nonahydrate is dissolved in 10g of ethanol to obtain a metal salt solution, then the metal salt solution and 10g of 70% zirconium n-propoxide solution are placed in a mortar for uniform mixing, the purity of the zirconium n-propoxide is analytically pure, then 20g of ammonium bicarbonate solid is rapidly added into the mortar, and the purity of the ammonium bicarbonate is analytically pure, thus obtaining the mixture.
S2, grinding the mixture obtained in the step S1 in air for 20min, and then placing the mixture in a 65 ℃ oven for drying treatment to obtain loose precursor powder.
In this example, the aluminum nitrate nonahydrate solution used for doping is acidic, and can undergo an acid-base neutralization reaction with an alkaline auxiliary agent to generate H 2 O and the corresponding solid precipitate, thereby doping the zirconium compound at the molecular layer. Specifically, the chemical reaction equation involved in the present embodiment is as follows:
Al(NO 3 ) 3 ·9H 2 O+3NH 4 HCO 3 →Al(OH) 3 +3CO 2 ↑+9H 2 O+3NH 4 NO 3 ；
Al(OH) 3 →AlOOH+H 2 O。
and S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1200 ℃, and the calcination time is 6 hours, so as to obtain the aluminum-doped zirconium dioxide powder.
Example 6 the preparation method of the zirconium dioxide powder of this example is substantially the same as example 5, and the specific implementation data are as follows:
s1, selecting a zirconium n-propoxide solution and a chromium nitrate nonahydrate solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
dissolving 0.3g of chromium nitrate nonahydrate in 3g of ethanol to obtain a metal salt solution, then placing the metal salt solution and 10g of 70% zirconium n-propoxide solution in a mortar for uniform mixing, wherein the purity of the zirconium n-propoxide is analytically pure, and then rapidly adding 10.3g of ammonium bicarbonate solid into the mortar, wherein the purity of the ammonium bicarbonate is analytically pure, so as to obtain the mixture.
S2, grinding the mixture obtained in the step S1 in air for 20min, and then placing the mixture in a drying oven at 75 ℃ for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1300 ℃, and the calcination time is 0.5h, so as to obtain the chromium-doped green zirconium dioxide powder.
Example 7 the preparation method of the zirconium dioxide powder of this example is substantially the same as example 5, and the specific implementation data are as follows:
s1, selecting a zirconium n-butoxide solution and an aluminum nitrate nonahydrate solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.3g of aluminum nitrate nonahydrate is dissolved in 3g of ethanol to obtain a metal salt solution, then the metal salt solution and 10g of 80% zirconium n-butoxide solution are placed in a mortar for uniform mixing, the purity of the zirconium n-butoxide is analytically pure, then 0.05g of ammonium bicarbonate solid is rapidly added into the mortar, and the purity of the ammonium bicarbonate is analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in air for 10min, and then placing the mixture in a 70 ℃ oven for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1500 ℃, and the calcination time is 2 hours, so that the aluminum-doped white zirconium dioxide powder is obtained.
Example 8 the preparation method of the zirconium dioxide powder of this example is substantially the same as example 5, and the specific implementation data are as follows:
s1, selecting a zirconium n-propoxide solution, an aluminum trichloride hexahydrate solution, a cobalt acetate tetrahydrate solution and a yttrium chloride hexahydrate solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.25g of aluminum trichloride hexahydrate, 0.31g of yttrium chloride hexahydrate and 0.15g of cobalt acetate tetrahydrate are dissolved in about 7g of ethanol to obtain a metal salt solution, then the metal salt solution and 5g of 80% zirconium n-butoxide solution are placed in a mortar for uniform mixing, the purity of the zirconium n-propoxide is analytically pure, and then 30g of ammonium bicarbonate solid is quickly added into the mortar, and the purity of the ammonium bicarbonate is analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in air for 30min, and then placing the mixture in an oven at 80 ℃ for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 into an electric furnace for calcination, wherein the calcination temperature is 1500 ℃, and the calcination time is 2 hours, so that the metal-doped blue zirconium dioxide powder is obtained.
The principle of the invention for preparing zirconium dioxide powder is as follows: firstly, the metal organic alkoxide has the advantage of easy impurity removal by a reduced pressure distillation mode, so that high-purity metal oxide can be further obtained, and the purity of zirconium dioxide powder is further improved. Moreover, the organic alkoxide of zirconium is extremely easily hydrolyzed and reacts with H 2 The O reaction activity is high. In the grinding or ball milling process, the zirconium alkoxide can absorb moisture in the air, so that hydrolysis reaction occurs to generate zirconium dioxide. In addition, the solid auxiliary agent is an ammonium salt substance which is easy to decompose by heating or friction, and in the grinding or ball milling process, the solid auxiliary agent decomposes water molecules, so that zirconium alkoxide is hydrolyzed, and meanwhile, the problem of too high hydrolysis reaction speed of the zirconium alkoxide can be avoided. The alcohol generated by the hydrolysis of zirconium alkoxide can act with the surface hydroxyl groups of the newly generated powder material, so that the hard agglomeration of large-particle products can be prevented; in addition, the solid auxiliary agent decomposes a large amount of ammonia and carbon dioxide, which is also helpful for eliminating hard agglomeration and dispersing powder, so that the prepared powder has uniform particles and small particle size. Furthermore, dopingThe metal salt solution is acidic and can be subjected to acid-base neutralization reaction with alkaline solid auxiliary agent to generate H 2 O and the corresponding solid precipitate, thereby doping the zirconium compound at the molecular layer. Although in the above examples only two solutions of zirconium n-propoxide and zirconium n-butoxide are used, in other examples, the types of zirconium alkoxides may be arbitrarily replaced and arbitrarily combined, and are not exemplified herein.
The invention takes the high-purity zirconium organic alkoxide solution as a zirconium source, takes a proper amount of solid ammonium carbonate or ammonium bicarbonate which is easy to decompose and the like as an auxiliary agent, can obtain precursor powder by grinding or ball milling in the air, can control the doping component of zirconium dioxide by adding the soluble metal salt solution, so as to improve the performance of zirconium dioxide-based ceramics, facilitate color mixing, avoid dispersing agents, simplify the operation, facilitate industrial production, avoid the suction filtration process of the traditional liquid phase precipitation method, and the obtained superfine zirconium dioxide powder has the advantages of narrow particle size distribution range, high purity, no hard agglomeration and the like.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples only represent preferred embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. A preparation method of zirconium dioxide powder is characterized in that: hydrolyzing the high-purity zirconium organic alkoxide by taking the decomposition products of water and solid auxiliaries in the air as water sources; the preparation method comprises the following steps:
mixing the first raw material and the second raw material, and rubbing and drying to obtain precursor powder; calcining the precursor powder to obtain zirconium dioxide powder;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or the first raw material comprises a high-purity zirconium organic alkoxide solution and a metal salt solution; the second raw material is a solid auxiliary agent which can be decomposed under the friction condition; the purity of the high-purity zirconium organic alkoxide solution is more than analytical purity;
the solid auxiliary agent comprises one or more of ammonium bicarbonate, ammonium carbonate or ammonium carbamate;
the metal salt is strong acid weak alkali salt and comprises one or more of yttrium chloride hexahydrate, erbium nitrate pentahydrate, aluminum nitrate nonahydrate, chromium nitrate nonahydrate, aluminum trichloride hexahydrate and cobalt acetate tetrahydrate;
the friction is that the mixture of the first raw material and the second raw material is ground for 10-720min in air;
the mass ratio of the second raw material to the first raw material is 0.05-6:1.
2. The method for producing a zirconium dioxide powder according to claim 1, wherein: the high-purity zirconium organic alkoxide comprises one or more of zirconium n-butoxide, zirconium isopropoxide, zirconium n-propoxide or zirconium ethoxide.
3. The method for producing a zirconium dioxide powder according to claim 1, wherein: when the first feedstock comprises a high purity zirconium organic alkoxide solution and a metal salt solution, the molar ratio of the metal salt to the zirconium source in the high purity zirconium organic alkoxide solution is from 0.001 to 0.5:1.
4. the method for producing a zirconium dioxide powder according to claim 1, wherein: the rubbing includes ball milling.
5. The method for producing a zirconium dioxide powder according to claim 1, wherein: the calcination temperature of the precursor powder ranges from 500 ℃ to 1500 ℃ and the calcination time ranges from 0.5h to 6h.
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| CN101597083A (en) * | 2009-06-29 | 2009-12-09 | 湘潭大学 | A kind of preparation method of monodisperse nano-titanium dioxide |
| CN101723468A (en) * | 2009-12-29 | 2010-06-09 | 浙江大学 | Method for preparing nanometer iron oxide red |
| CN102358826A (en) * | 2011-08-19 | 2012-02-22 | 永州皓志稀土材料有限公司 | Method for preparing aluminum-doped zirconium oxide compound polishing powder |
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