CN114538508A - Zirconium dioxide powder and preparation method thereof - Google Patents
Zirconium dioxide powder and preparation method thereof Download PDFInfo
- Publication number
- CN114538508A CN114538508A CN202210192764.XA CN202210192764A CN114538508A CN 114538508 A CN114538508 A CN 114538508A CN 202210192764 A CN202210192764 A CN 202210192764A CN 114538508 A CN114538508 A CN 114538508A
- Authority
- CN
- China
- Prior art keywords
- zirconium
- purity
- raw material
- dioxide powder
- powder
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 110
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 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
- 239000000243 solution Substances 0.000 claims abstract description 42
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000001354 calcination Methods 0.000 claims abstract description 35
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 13
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZWAPSEBBXULIEX-UHFFFAOYSA-N C(C)(C)[Zr] Chemical compound C(C)(C)[Zr] ZWAPSEBBXULIEX-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZPGIVLOUVWCNHK-UHFFFAOYSA-N C(CC)[Zr] Chemical compound C(CC)[Zr] ZPGIVLOUVWCNHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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
- 238000000034 method Methods 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 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
- 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
- 239000002253 acid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 33
- 239000000203 mixture Substances 0.000 description 28
- 239000004570 mortar (masonry) Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 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 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- -1 zirconium alkoxide Chemical class 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000007062 hydrolysis Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000011351 dental ceramic Substances 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
- 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 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
- 239000011819 refractory material 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
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- 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 obtaining precursor powder after friction and drying; 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 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 n-butyl zirconium, isopropyl zirconium, n-propyl zirconium or zirconium ethoxide. The solid auxiliary agent comprises more than one of ammonium bicarbonate, ammonium carbonate or ammonium carbamate. Also provides the zirconium dioxide powder prepared by the preparation method. The preparation method of the zirconium dioxide powder provided by the invention has the advantages of simple steps and loose preparation conditions, and the prepared zirconium dioxide powder has the advantages of uniform particle size, small particles, less 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 (ZrO2) powder has become an important dental ceramic, refractory material and catalytic material because of its melting point as high as 2700 ℃, high electrical resistivity, low thermal conductivity (1000 ℃,2.09W/(m · K)), high expansion coefficient, and excellent mechanical properties, and because of its readily available raw materials, low toxicity and stable chemical properties.
At present, the main preparation approaches 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, for example, the traditional coprecipitation method is easy to form jelly in the preparation process, 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 preparation temperature and pressure are strict, and a filtration step is finally required; 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 easily causes uneven powder particles; the reaction speed of the alkoxide hydrolysis method is high, the control is not easy, 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 that the reaction conditions are not easy to control, the industrial production is difficult, and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides zirconium dioxide powder and a preparation method thereof, so that the problems of more impurities, nonuniform powder particles, harsh reaction conditions, complex preparation process and the like of the zirconium dioxide powder in the prior art are solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of zirconium dioxide powder comprises the following steps:
mixing the first raw material and the second raw material, and obtaining precursor powder after friction and drying; calcining the precursor powder to obtain the zirconium dioxide powder;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or 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 further improvement of the technical scheme is as follows:
the high-purity zirconium organic alkoxide comprises one or more of n-butyl zirconium, isopropyl zirconium, n-propyl zirconium 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 raw material 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 0.001-0.5: 1.
the purity of the high-purity zirconium organic alkoxide solution is higher than analytical purity.
The rubbing comprises grinding or ball milling; the friction time is 10-720 min.
The calcining temperature range of the precursor powder is 500-1500 ℃, and the calcining time is 0.5-6 h.
The metal salt is strong acid weak base 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 the zirconium dioxide powder prepared by the preparation method.
According to the technical scheme, the preparation method of the zirconium dioxide powder takes the zirconium alkoxide which is easy to purify as a zirconium source, and takes the water in the air and the decomposition product of the solid auxiliary agent as the H2O source to hydrolyze the zirconium alkoxide, the reaction process involves three phases of solid, liquid and gas, the preparation method is simple in process, loose in reaction condition and low in energy consumption, is suitable for industrial production, reduces the filtering steps of powder preparation by a coprecipitation method and a hydrothermal method, effectively prevents the hard agglomeration phenomenon of the powder, and the prepared powder product is high in particle uniformity, small in particle size and high in 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 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 zirconium dioxide powder prepared in example 4 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying 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 in the description of the invention herein 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 method for preparing zirconium dioxide powder according to the embodiment of the present invention includes the following steps:
s1, adding a proper amount of second raw material into the first raw material to obtain a mixture of the two raw materials;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or 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 n-butyl zirconium, isopropyl zirconium, n-propyl zirconium or zirconium ethoxide; the purity of the high-purity zirconium organic alkoxide solution is higher 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 raw material 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 0.001-0.5: 1; the metal salt is strong acid weak base 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, for example, 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 may decompose the residual solid auxiliary agent.
The duration of grinding or ball milling of the mixture in the air does not directly affect the crystalline phase of the zirconium dioxide powder, and longer friction time is more beneficial to forming precursor powder with smaller particle size, so that the particle size is more uniform.
S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcining, and thus obtaining the zirconium dioxide powder. The calcination temperature range is 500-1500 ℃, for example, the calcination temperature can be 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, etc.; the calcination time is 0.5h to 6h, for example, the calcination time can be 1h, 2h, 3h, 4h, 5h, and the like.
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 needs.
Example 1, the preparation method of the zirconium dioxide powder of this example is consistent with the above steps, and the specific implementation data is as follows:
s1, selecting a normal butanol zirconium solution as a first raw material, and selecting ammonium carbonate as a second raw material;
firstly, 10g of commercial solution of 80 percent by mass of zirconium n-butyl alcohol is put into an agate mortar, the purity of the zirconium n-butyl alcohol is analytically pure, and then 10g of solid ammonium carbonate is added into the agate mortar, and the purity of the ammonium carbonate is also analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in air for 30min, wherein in the grinding process, the n-butyl alcohol zirconium continuously absorbs the moisture in the air and the ammonium carbonate is decomposed ((NH)4)2CO3→2NH3↑+H2O↑+CO2℃) resulting in the continuous hydrolysis thereof (Zr (OR)4+4H2O→Zr(OH)4↓ +4HOR ×); meanwhile, the solvent in the n-butyl zirconium solution gradually volatilizes, and the mixture slowly changes from a pasty state to loose white powder. And (3) drying the white powder in an oven at 80 ℃ to decompose residual ammonium carbonate to obtain loose precursor powder.
S3, calcining the precursor powder prepared in the step S2 in an electric furnace at 1150 ℃ for 2h to obtain white zirconium dioxide powder (Zr (OH)4→ZrO2+2H2O)。
FIG. 2 is an XRD pattern of the zirconium dioxide powder obtained in example 1, and it can be seen from FIG. 2 that the diffraction peak is sharp and similar to that of monoclinic zirconium dioxide (ZrO)2) Standard card (JCPDS: 88-2390), indicating that the product prepared by the method of this example is highly crystalline monoclinic zirconia.
FIG. 3 is a particle size distribution diagram of the zirconium dioxide powder obtained in example 1, and it can be seen from FIG. 3 that the powder has a narrow particle size distribution range, which shows that the uniformity of the particle size is high, and the diameter D is501.189 μm, belonging to superfine powder.
Example 2, the preparation method of the zirconium dioxide powder of this example is substantially the same as example 1, and the specific implementation data is as follows:
s1, selecting a n-butyl alcohol zirconium solution as a first raw material, and selecting ammonium bicarbonate as a second raw material;
firstly, 15.2g of commercially available solution of 80 percent by mass of zirconium n-butyl alcohol is put into a ball milling tank, the purity of the zirconium n-butyl alcohol 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, the n-butyl alcohol zirconium continuously absorbs water in the air and water generated by decomposition of ammonium bicarbonate to cause continuous hydrolysis of the mixture; meanwhile, the solvent in the n-butyl zirconium solution gradually volatilizes, and the mixture slowly changes from a pasty state to loose white powder. And (3) drying the white powder in an oven at 80 ℃ to decompose the residual ammonium bicarbonate to obtain loose precursor powder.
And S3, calcining the precursor powder prepared in the step S2 in an electric furnace at the temperature of 600 ℃ for 2h to obtain the white zirconium dioxide powder.
FIG. 4 is an XRD pattern of the zirconium dioxide powder obtained in example 2, and it can be seen from FIG. 4 that the obtained white ultrafine powder is zirconium dioxide powder. In order to study that the powder has a porous structure, the powder was subjected to a nitrogen adsorption test, and the specific surface area of the zirconium dioxide powder was found to be 33.1m2Per g, pore volume of 0.0874cm3In terms of/g, the mean pore diameter is 10.7 nm. FIG. 5 is a nitrogen adsorption isotherm of the powder, which can be shown by the hysteresis loop in FIG. 5The 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 is as follows:
s1, selecting a normal butyl zirconium solution and a yttrium chloride hexahydrate solution as first raw materials, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.63g of yttrium chloride hexahydrate is dissolved in about 3g of ethanol to obtain a metal salt solution, then the metal salt solution and 10.63g of a commercial solution of zirconium n-butyl alcohol with the mass fraction of 80% are placed in a mortar and uniformly mixed, the purity of the zirconium n-butyl alcohol is analytically pure, and then 10.63g of ammonium bicarbonate solid is rapidly added into the mortar (the rapid addition aims to enable the ammonium bicarbonate to be in contact with zirconium alkoxide as soon as possible), and the purity of the ammonium bicarbonate is also analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in the air for 10min, and gradually changing the mixture from pasty to loose white powder. And (3) drying the white powder in a drying oven at 60 ℃ to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcination, wherein the calcination temperature is 1200 ℃, and the calcination time is 2h, so that the yttrium-doped white zirconium dioxide powder is obtained.
FIG. 6 is an XRD pattern of the zirconium dioxide powder obtained in example 3, and it can be seen from FIG. 6 that the diffraction intensity is decreased, which shows that the crystallinity of the powder is decreased after doping yttrium metal, and yttrium is doped successfully.
Example 4, the preparation method of the zirconium dioxide powder of this example is substantially the same as example 3, and the specific implementation data is as follows:
s1, selecting a normal butyl alcohol zirconium solution and an erbium nitrate pentahydrate solution as first raw materials, and selecting ammonium bicarbonate and ammonium carbonate as second raw materials;
firstly, 0.4g of erbium nitrate pentahydrate is dissolved in about 3g of methanol to obtain a metal salt solution, then the metal salt solution and 10g of an 80% by mass n-butyl zirconium solution are placed in a mortar and uniformly mixed, the purity of the zirconium n-propoxide is analytically pure, then 5.4g of ammonium bicarbonate and 5g of ammonium carbonate solid are rapidly added into the mortar, and the purity of the ammonium bicarbonate and the purity of the ammonium carbonate are analytically pure, so that the mixture is obtained.
S2, grinding the mixture obtained in the step S1 in air for 20min, and then placing the mixture in an oven at 70 ℃ for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcination, wherein the calcination temperature is 1150 ℃ and the calcination time is 2h, so that the erbium-doped rose gold zirconium dioxide powder is obtained.
FIG. 7 is an XRD pattern of the zirconium dioxide powder obtained in example 4, and it can be seen 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 is as follows:
s1, selecting a zirconium n-propoxide solution and an aluminum nitrate nonahydrate solution as first raw materials, and selecting ammonium bicarbonate as a second raw material;
dissolving 3.91g of aluminum nitrate nonahydrate in 10g of ethanol to obtain a metal salt solution, uniformly mixing the metal salt solution and 10g of 70% zirconium n-propoxide solution in a mortar, wherein the purity of the zirconium n-propoxide is analytically pure, and quickly adding 20g 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 an oven at 65 ℃ for drying treatment to obtain loose precursor powder.
In the embodiment, the aluminum nitrate nonahydrate solution used for doping is acidic, and can perform acid-base neutralization reaction with an alkaline auxiliary agent to generate H2O and corresponding solid precipitates, thereby doping the zirconium compound at the molecular layer surface. Specifically, the chemical reaction equation involved in this embodiment is as follows:
Al(NO3)3·9H2O+3NH4HCO3→Al(OH)3+3CO2↑+9H2O+3NH4NO3；
Al(OH)3→AlOOH+H2O。
and S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcination, wherein the calcination temperature is 1200 ℃, and the calcination time is 6 hours, so that the aluminum-doped zirconium dioxide powder is obtained.
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 is as follows:
s1, selecting a zirconium n-propoxide solution and a chromium nitrate nonahydrate solution as first raw materials, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.3g of chromium nitrate nonahydrate is dissolved in about 3g of ethanol to obtain a metal salt solution, then the metal salt solution and 10g of 70% zirconium n-propoxide solution are uniformly mixed in a mortar, the purity of the zirconium n-propoxide is analytically pure, then 10.3g of ammonium bicarbonate solid is rapidly added in 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 20min, and then placing the mixture in a 75 ℃ oven for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcination, wherein the calcination temperature is 1300 ℃, and the calcination time is 0.5h, so that the green chromium-doped zirconium dioxide powder is obtained.
Example 7, the preparation method of the zirconium dioxide powder of the present embodiment is substantially the same as that of example 5, and the specific implementation data is as follows:
s1, selecting a normal butyl alcohol zirconium solution and an aluminum nitrate nonahydrate solution as first raw materials, and selecting ammonium bicarbonate as a second raw material;
firstly, 0.3g of aluminum nitrate nonahydrate is dissolved in about 3g of ethanol to obtain a metal salt solution, then the metal salt solution and 10g of an n-butyl zirconium solution with the mass fraction of 80% are placed in a mortar and uniformly mixed, the purity of the n-butyl zirconium is analytically pure, and 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 an oven at 70 ℃ for drying treatment to obtain loose precursor powder.
And S3, placing the precursor powder prepared in the step S2 in an electric furnace for calcination, wherein the calcination temperature is 1500 ℃, and the calcination time is 2h, 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 is 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 first raw materials, 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 an n-butyl zirconium solution with the mass fraction of 80% are placed in a mortar and uniformly mixed, the purity of zirconium n-propoxide is analytically pure, and then 30g of ammonium bicarbonate solid is rapidly added into the mortar, and the purity of ammonium bicarbonate is analytically pure, so that the mixture is obtained.
And 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 in an electric furnace for calcination, wherein the calcination temperature is 1500 ℃, and the calcination time is 2h, 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 through a reduced pressure distillation mode, so that high-purity metal oxide can be further obtained, and the purity of the zirconium dioxide powder is further improved. Furthermore, the organic alkoxides of zirconium are very easily hydrolyzed with H2The O reaction activity is high. In the process of grinding or ball milling, zirconium alkoxide can absorb moisture in air, so that hydrolysis reaction is carried out to generate the zirconium alkoxideZirconia (zirconium oxide). In addition, the solid auxiliary agent is ammonium salt substance which is easy to decompose by heating or friction, and during the grinding or ball milling process, the solid auxiliary agent decomposes water molecules, so that zirconium alkoxide is hydrolyzed, and the problem of too high hydrolysis reaction speed of the zirconium alkoxide can be avoided. Alcohol generated by hydrolysis of zirconium alkoxide can react with surface hydroxyl of a newly generated powder material, and hard agglomeration of large-particle products can be prevented; in addition, the solid assistant decomposes a large amount of ammonia and carbon dioxide, and is also helpful for eliminating hard agglomeration and dispersing powder, so that the prepared powder has uniform particles and small particle size. In addition, the metal salt solution used for doping is acidic and can be subjected to acid-base neutralization reaction with alkaline solid auxiliary agent to generate H2O and corresponding solid precipitates, thereby doping the zirconium compound at the molecular layer surface. Although only two solutions of zirconium n-propoxide and zirconium n-butoxide are used in the above examples, the types of zirconium alkoxides may be arbitrarily replaced and combined in other examples, which are not necessarily listed herein.
The invention takes high-purity zirconium organic alkoxide solution as a zirconium source, takes a proper amount of easily-decomposed solid ammonium carbonate or ammonium bicarbonate and the like as auxiliary agents, and can obtain precursor powder by grinding or ball milling in the air, and the doping components of the zirconium dioxide can be controlled by adding soluble metal salt solution, so that the performance of the zirconium dioxide-based ceramic is improved, the color mixing is convenient, no dispersant is needed, the operation is simple, the industrial production is easy, the suction filtration process of the traditional liquid phase precipitation method is avoided, 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 can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of zirconium dioxide powder is characterized by comprising the following steps: the method comprises the following steps:
mixing the first raw material and the second raw material, and obtaining precursor powder after friction and drying; calcining the precursor powder to obtain the zirconium dioxide powder;
wherein the first raw material is a high-purity zirconium organic alkoxide solution or 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.
2. The method according to claim 1, wherein: the high-purity zirconium organic alkoxide comprises one or more of n-butyl zirconium, isopropyl zirconium, n-propyl zirconium or zirconium ethoxide.
3. The method according to claim 1, wherein: the solid auxiliary agent comprises one or more of ammonium bicarbonate, ammonium carbonate or ammonium carbamate.
4. The method according to any one of claims 1 to 3, wherein: the mass ratio of the second raw material to the first raw material is 0.05-6: 1.
5. The method according to claim 1, wherein: when the first raw material 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 0.001-0.5: 1.
6. the method according to claim 1, wherein: the purity of the high-purity zirconium organic alkoxide solution is higher than analytical purity.
7. The method according to claim 1, wherein: the rubbing comprises grinding or ball milling; the friction time is 10-720 min.
8. The method according to claim 1, wherein: the calcining temperature range of the precursor powder is 500-1500 ℃, and the calcining time is 0.5-6 h.
9. The method according to claim 1, wherein: the metal salt is strong acid weak base 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.
10. Zirconium dioxide powder, characterized in that: prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210192764.XA CN114538508B (en) | 2022-02-28 | 2022-02-28 | Zirconium dioxide powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210192764.XA CN114538508B (en) | 2022-02-28 | 2022-02-28 | Zirconium dioxide powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114538508A true CN114538508A (en) | 2022-05-27 |
| CN114538508B CN114538508B (en) | 2023-12-26 |
Family
ID=81661777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210192764.XA Active CN114538508B (en) | 2022-02-28 | 2022-02-28 | Zirconium dioxide powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114538508B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102689925A (en) * | 2011-12-06 | 2012-09-26 | 南昌大学 | Methanol thermosynthesis method for preparing stable spherical tetragonal phase rare-earth yttrium zirconium oxide |
-
2022
- 2022-02-28 CN CN202210192764.XA patent/CN114538508B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102689925A (en) * | 2011-12-06 | 2012-09-26 | 南昌大学 | Methanol thermosynthesis method for preparing stable spherical tetragonal phase rare-earth yttrium zirconium oxide |
Non-Patent Citations (2)
| Title |
|---|
| 张建成等: ""醇盐锆水解制备 ZrO2 粉体的研究"", 《硅酸盐通报》, no. 5, pages 31 - 35 * |
| 戴健等: ""醇盐水解法制备的纳米级稳定氧化锆细粉"", 《无机材料学报》, vol. 8, no. 1, pages 51 - 56 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114538508B (en) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Laberty-Robert et al. | Powder synthesis of nanocrystalline ZrO2–8% Y2O3 via a polymerization route | |
| Li et al. | Characterization and sintering of nanocrystalline CeO2 powders synthesized by a mimic alkoxide method | |
| CN102295304B (en) | Preparation method of pseudo-boehmite and microcrystalline corundum abrasive | |
| US6030914A (en) | Zirconia fine powder and method for its production | |
| CN102173775B (en) | Method for preparing neodymium-doped yttrium aluminum garnet micro/nano powder by spray freeze-drying | |
| Li et al. | A homogeneous co-precipitation method to synthesize highly sinterability YAG powders for transparent ceramics | |
| JPS6256322A (en) | Composition based on ceric oxide, manufacture and use | |
| CN108511797B (en) | Li7La3Zr2O12Solid electrolyte preparation method | |
| CN101302019A (en) | Method for preparing rare earth-doped yag nano-powder by partial liquid phase precipitation method | |
| Muliuoliene et al. | Evidence of the formation of mixed-metal garnets via sol–gel synthesis | |
| RU2349550C2 (en) | Method of preparing zirconium oxides and zirconium based mixed oxides | |
| CN103647097A (en) | Sc2O3-stabilized ZrO2-based electrolyte powder and preparation method thereof, and Sc2O3-stabilized ZrO2 electrolyte ceramic wafer prepared from powder | |
| Wang et al. | Direct Formation of Crystalline Gadolinium‐Doped Ceria Powder via Polymerized Precursor Solution | |
| Osman et al. | Chelating agent size effect on thermal decomposition, phase formation and morphology characteristics of Y3+ doped Ba (Ce, Zr) O3 ceramics powder prepared by a sol-gel process | |
| CN114538508B (en) | Zirconium dioxide powder and preparation method thereof | |
| CN106268612B (en) | A kind of porous barium strontium titanate raw powder's production technology | |
| CN104528814A (en) | Preparation method and product of CaTi2O4(OH)4 diamond nanosheet with lamellar structure | |
| CN112573570A (en) | Scandium-cerium-doped zirconium oxide superfine powder and preparation method thereof | |
| CN1295976A (en) | Method for producing high-activity super fine grain barium titanate | |
| KR20150088409A (en) | Method of forming a gdc/lscf composite powder | |
| CN107721423A (en) | A kind of method that co-precipitation prepares yttrium oxide transparent ceramic | |
| Gongyi et al. | Effect of Preparation Methods and Condition of Precursors on the Phase Composition of Yttria‐Stabilized Zirconia Powders | |
| JP4061679B2 (en) | Zirconia fine powder and method for producing the same | |
| CN109574050B (en) | Preparation of aluminum ammonium carbonate with ultrahigh specific surface area and method for preparing aluminum oxide by thermal decomposition of aluminum ammonium carbonate | |
| Feng et al. | Green synthesis of ceria powders with special physical properties by carbon dioxide carbonization |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |