CN111377737B - Tetragonal phase nano-doped zirconia ceramic powder material and preparation method thereof - Google Patents
Tetragonal phase nano-doped zirconia ceramic powder material and preparation method thereof Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000843 powder Substances 0.000 title claims abstract description 48
- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 23
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 27
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 15
- 150000003754 zirconium Chemical class 0.000 description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
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- 238000000227 grinding Methods 0.000 description 7
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- 239000004094 surface-active agent Substances 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
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- 230000002776 aggregation Effects 0.000 description 3
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- 239000008367 deionised water Substances 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
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- 230000001788 irregular Effects 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
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- YKPHFLCWBWVURW-UHFFFAOYSA-N 2-methylpropan-1-ol;zirconium Chemical compound [Zr].CC(C)CO YKPHFLCWBWVURW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal oxalate Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001959 inorganic nitrate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- BBMRFTLCEAZQEQ-UHFFFAOYSA-N oxalic acid;oxozirconium Chemical compound [Zr]=O.OC(=O)C(O)=O BBMRFTLCEAZQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- JMTCDHVHZSGGJA-UHFFFAOYSA-M potassium hydrogenoxalate Chemical compound [K+].OC(=O)C([O-])=O JMTCDHVHZSGGJA-UHFFFAOYSA-M 0.000 description 1
- GANDVAJEIJXBQJ-UHFFFAOYSA-M potassium;hydron;2-hydroxy-2-oxoacetate Chemical compound [K+].OC(=O)C(O)=O.OC(=O)C([O-])=O GANDVAJEIJXBQJ-UHFFFAOYSA-M 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- UJRAXLUXHBUNDO-UHFFFAOYSA-M sodium;hydron;oxalate Chemical compound [Na+].OC(=O)C([O-])=O UJRAXLUXHBUNDO-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BYRDOLUXMVYFQM-UHFFFAOYSA-N triazanium 2-hydroxy-2-oxoacetate oxalate Chemical compound C(C(=O)[O-])(=O)[O-].[NH4+].C(C(=O)O)(=O)[O-].[NH4+].[NH4+] BYRDOLUXMVYFQM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- C04B35/01—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
- C04B35/486—Fine ceramics
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- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract
The invention relates to a tetragonal-phase nano-doped zirconia ceramic powder material and a preparation method thereof, wherein the material isThe doped zirconia nano ceramic powder with irregular-shaped tetragonal crystal phase structure comprises 1-5 wt% of doping elements in percentage by mass, the particle size of the material is 50-100nm, the particle size D50 is less than 100nm after drying and crushing treatment, and the specific surface area is 3-10m 2 (ii) in terms of/g. Compared with the prior art, the preparation process of the invention has simple operation, does not need additional complex conditions and complex equipment, can react at normal temperature and normal pressure, and has cheap and easily obtained practical raw materials, thereby leading the preparation cost of the material to be relatively lower, leading the particle size to be smaller and leading the prepared zirconia to be used for preparing electronic ceramic devices, appearance ceramic devices and other multiple purposes.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a tetragonal-phase nano-doped zirconia ceramic powder material with the particle size D50 of less than 100nm and a preparation method thereof.
Background
Zirconia-based ceramics are common ceramic materials with good application performance in daily life, and have been widely applied to the fields of electronic information, articles for daily use, biological medicine and the like. But with the expansion of the application field and the improvement of performance indexes, the requirement on the performance of the zirconia is higher and higher. The performance of zirconia ceramic powder is the fundamental factor for determining the zirconia ceramic products obtained by processing in the future, so in order to obtain high-performance zirconia ceramic products, zirconia ceramic powder products with excellent performance are prepared, and zirconia-based ceramic powder materials have become the key point of research in the material field. For example, the mechanical property and the thermal sintering property can be improved by doping some elements. The purity, particle size, surface property, shape and other characteristics of the zirconia ceramic powder directly determine the yield and subsequent use performance of the ceramic device in the processing process of the ceramic device. Therefore, the preparation of the high-quality zirconia nano ceramic powder is the current research hotspot and technical difficulty. However, the ceramic powder particles prepared by the conventional preparation method are often large, and even if the particle size can reach the nanometer level, the product is always seriously agglomerated or the crystal phase is impure after drying treatment, so that the development and application of the zirconia ceramic material are greatly limited. The preparation of high-quality nano-grade zirconia ceramic powder and the structure control thereof are key technical problems for determining the application of zirconia ceramic.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a tetragonal phase nano-doped zirconia ceramic powder material with the particle size D50 being less than 100nm and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: a tetragonal phase nano-doped zirconia ceramic powder material is characterized in that the material is doped zirconia nano-ceramic powder with an irregular tetragonal phase structure, the mass percentage content of doping elements is 1-5 wt%, the particle size of the material is 50-100nm, the particle size D50 is less than 100nm after drying and crushing treatment, the D90 is less than 300nm, and the specific surface area is 3-10m 2 /g。
The invention provides a preparation method of a tetragonal-phase nano-doped zirconia ceramic powder material with the particle size D50 less than 100nm, which comprises the following steps: firstly, dissolving zirconium salt of a zirconium oxide precursor, salt containing doping elements and a certain amount of surfactant, slowly introducing oxalate aqueous solution into the mixed solution, carrying out a liquid-phase precipitation reaction process, carrying out subsequent centrifugation, washing, drying and roasting treatment to obtain tetragonal-phase zirconium oxide nano ceramic powder, and then carrying out gas grinding treatment to obtain the tetragonal-phase nano doped zirconium oxide ceramic powder material with the particle size D50 of less than 100 nm. The method comprises the following specific steps:
(1) dissolving a certain amount of zirconium salt precursor, salt containing doping elements and a surfactant into a mixed solvent of water and organic alcohol (the volume ratio of water to organic alcohol is 1: 0.1-1), mechanically stirring to obtain a clear solution, and recording the clear solution as a solution A.
(2) A quantity of oxalate salt was weighed into a volume of deionized water solution and designated as solution B.
(3) And uniformly mixing the solution A and the solution B by adopting a peristaltic pump in a forward addition, reverse addition or parallel flow mode respectively, reacting at room temperature, continuously stirring for 1-2 days to obtain a white gel solution, carrying out centrifugal separation to obtain a white precipitate product, washing, drying and roasting, and finally carrying out gas-state grinding treatment on the obtained solid powder sample to obtain the tetragonal crystal phase nano-doped zirconia ceramic powder material with the particle size D50 of less than 100 nm.
In the invention, the precursor zirconium salt is subjected to a precipitation reaction in the presence of oxalate to generate the zirconyl oxalate sol precipitate, and the organic alcohol can weaken the interaction among sol particles and change the surface state of the corresponding oxalic acid precipitate, thereby effectively preventing the occurrence of agglomeration among the precipitate particles and having an effective regulation and control effect on the zirconia crystal phase. Therefore, the tetragonal-phase nano-doped zirconia ceramic powder material with the particle size D50 smaller than 100nm can be obtained through a simpler treatment process.
The concentration of a zirconium salt precursor in a reaction system formed by the solution A and the solution B is 1-10 wt%, and the mass percentage content of doping elements is 1-5 wt%; the mass ratio of the zirconium salt precursor to the oxalate is 0.8-1.5: 1; the reaction temperature can be controlled in the range of 5-40 ℃ under the condition of room temperature, namely, with season change.
The zirconium salt precursor is inorganic zirconium salt or organic zirconate which can be dissolved in water and organic alcohol; the calcium salt precursor is one or more of zirconium oxychloride, zirconyl nitrate, zirconium acetylacetonate, zirconium n-propoxide, zirconium isopropoxide, zirconium isobutanol and zirconium n-butanol;
the salt containing the doping elements is rare earth element inorganic nitrate matched with a zirconia crystal phase structure; the salt containing the doping elements is one or more of yttrium nitrate, cerium nitrate, ammonium ceric nitrate, ytterbium nitrate, gadolinium nitrate, neodymium nitrate, holmium nitrate and lanthanum nitrate;
the surfactant is mainly nonionic high molecular polymer; the surfactant is one or more of polyethylene glycol, PVP, polyacrylic acid, polyether and F127; the mass ratio of the zirconium salt precursor to the surfactant is 10: 0.2-1.
The oxalate is mainly alkali metal oxalate or ammonium oxalate; the oxalate is one or more of ammonium oxalate, ammonium hydrogen oxalate, sodium hydrogen oxalate, potassium oxalate and potassium hydrogen oxalate;
the organic alcohol is liquid straight-chain alkyl alcohol or isomer alcohol thereof; the organic alcohol is one or more of ethanol, methanol, propanol, isopropanol, n-butanol and benzyl alcohol.
The water is obtained by water purification treatment, wherein the content of heavy metal ions, iron, cobalt and nickel ions is less than ppm.
The solution A and the solution B are placed in containers and reaction containers which are glass containers, organic plastic containers or ceramic enamel containers and comprise one or more of glass flasks, glass beakers, watch glasses, conical flasks, wide-mouth bottles, weighing bottles, test tubes, measuring cups, plastic beakers, ceramic reaction kettles, enamel reaction kettles and centrifugal tubes.
The centrifugal speed of the centrifugal separation in the step (3) is 5000-.
And (3) selecting one or more solvents from water, methanol, ethanol and isopropanol for washing.
The temperature range selected for drying treatment in the step (3) is 60-150 ℃; the temperature range for roasting treatment is 600-1100 ℃, the roasting time is 3-5 h, the adopted atmosphere is air atmosphere, and air needs to be continuously blown in by an air compressor.
The selected equipment for gaseous grinding treatment of the solid powder sample is an airflow pulverizer, the power is 4KW, the powder product is collected through a cyclone separator, the power of an air compressor is 50KW, and 1.0Mpa compressed air is provided for pulverization.
Compared with the prior art, the zirconium oxalate sol is generated by the reaction of a zirconium salt precursor and oxalate in a mixed solvent of water and organic alcohol, the organic alcohol plays a vital role in a reaction system, the existence of the zirconium oxalate sol can weaken the interaction among sol particles and change the surface state of corresponding oxalic acid precipitates, so that the occurrence of agglomeration among the precipitated particles is prevented, in addition, the crystal phase structure of zirconium oxide is effectively regulated and controlled, and the subsequent gas crushing technology can effectively remove the agglomeration of particles in the product and effectively control the particle size distribution in the product. The whole preparation reaction process is carried out under the static condition at room temperature, the nano-doped zirconia ceramic powder obtained by energy conservation and environmental protection has irregular particle appearance, uneven surface, good particle dispersibility, uniform granularity and smaller particle size, has wide application prospect, and is particularly suitable for the field of processing ceramic devices in the electronic information industry.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the tetragonal-phase nano-doped zirconia powder having a particle size D50 of less than 100nm obtained by the present preparation method, obtained in example 1.
FIG. 2 is a characteristic large angle X-ray spectrum of a tetragonal nano-doped zirconia powder having a monodispersed particle size D50 of less than 100nm, obtained in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Dissolving 10g of zirconium oxychloride, 0.1g of yttrium nitrate and 1.0g of PEG-10000 by using 500ml of a mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), stirring for half an hour, adding 400ml of an aqueous solution containing 10g of ammonium oxalate into the solution by using a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to obtain white gel, washing twice by using water and ethanol, drying in the air at 60 ℃ for 12 hours, calcining at 1000 ℃ for 4 hours, treating by using a gaseous pulverizer with the gas pressure of 1.0MPa, and collecting a powder sample by using a cyclone separator to obtain the tetragonal-doped nano zirconium oxide ceramic powder with the D50 of 90 nm. The morphology and characteristics are shown in fig. 1-2.
Example 2
Dissolving 10g of zirconium oxychloride, 0.1g of yttrium nitrate and 1.0g of PEG-10000 by using 500ml of mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), stirring for half an hour, adding 400ml of aqueous solution containing 10g of ammonium oxalate into the above solution by using a peristaltic pump, stirring for 12, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to separate white gel, then washing twice by using water and ethanol, drying in the air at 60 ℃ for 12 hours, and calcining at 1000 ℃ for 4 hours to obtain the tetragonal-doped nano zirconia ceramic powder with the D50 of 2.5 mu m.
Example 3
Dissolving 10g of zirconium oxychloride, 0.1g of yttrium nitrate and 1.0g of PEG-10000 by using 500ml of a mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), stirring for half an hour, then slowly dripping the solution into 400ml of an aqueous solution containing 10g of ammonium oxalate by using a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to obtain white gel, then washing twice by using water and ethanol respectively, drying in the air at 60 ℃ for 12 hours, calcining at 1000 ℃ for 4 hours, then treating by using a gas pulverizer with the gas pressure of 1.0MPa, and collecting the obtained powder sample by using a cyclone separator to obtain the tetragonal-doped nano zirconium oxide ceramic powder with the D50 of 95 nm.
Example 4
Dissolving 10g of zirconium oxychloride, 0.1g of cerium nitrate and 1.0g of PEG-10000 by using 500ml of mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.2), stirring for half an hour, adding 400ml of aqueous solution containing 10g of ammonium oxalate into the above solution by using a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to separate and obtain slightly yellowish gel, then washing twice by using water and ethanol respectively, drying in the air at 60 ℃ for 12 hours, calcining at 1000 ℃ for 4 hours, treating by using a gas pulverizer with the gas pressure of 1.0MPa, and collecting the obtained powder sample by using a cyclone separator to obtain the tetragonal-doped nano zirconium oxide ceramic powder with the D50 of 90 nm.
Example 5
Dissolving 10g of zirconium oxychloride, 0.1g of cerium nitrate and 1.0g of PVP (K30) by using 500ml of a mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), stirring for half an hour, adding 400ml of an aqueous solution containing 10g of ammonium oxalate into the solution by using a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to obtain slightly creamy yellow gel, then washing twice by using water and ethanol respectively, drying in the air at 60 ℃ for 12 hours, calcining at 1000 ℃ for 4 hours, treating by using a gas pulverizer with the gas pressure of 1.0MPa, and collecting the obtained powder sample by using a cyclone separator to obtain the tetragonal-doped nano zirconium oxide ceramic powder with the D50 of 90 nm.
Example 5
The preparation method of the tetragonal phase nano-doped zirconia ceramic powder material with the particle size D50 of less than 100nm comprises the following specific steps:
(1) dissolving a certain amount of zirconium salt precursor zirconium acetylacetonate, doping element-containing ceric ammonium nitrate and a surfactant PVP into a mixed solvent of water and organic alcohol n-butanol (the volume ratio of water to organic alcohol is 1:0.1), and mechanically stirring to obtain a clear solution, wherein the solution is marked as solution A.
(2) A quantity of oxalate potassium oxalate was weighed and dissolved in a volume of deionized water solution and designated as solution B. The mass ratio of the zirconium salt precursor to the oxalate is 0.8: 1;
(3) and (2) uniformly mixing the solution A and the solution B by adopting a peristaltic pump in a forward addition, reverse addition or parallel flow mode respectively, reacting at room temperature, wherein the concentration of a zirconium salt precursor in a formed reaction system is 1 wt%, the mass percentage content of the doping elements is 1 wt%, then continuously stirring for 1 day to obtain a white gel solution, and performing centrifugal separation to obtain a white precipitate product, wherein the centrifugal speed of the centrifugal separation is 5000rpm, and the centrifugal time is 10min each time. Washing with water, drying at 150 ℃, roasting at 1100 ℃ for 3hh, and finally performing gaseous grinding treatment on the obtained solid powder sample to obtain the tetragonal-phase nano-doped zirconia ceramic powder material with the granularity D50 less than 100 nm. The selected equipment for gaseous grinding treatment of the solid powder sample is an airflow pulverizer, the power is 4KW, the powder product is collected through a cyclone separator, the power of an air compressor is 50KW, and 1.0Mpa compressed air is provided for pulverization.
Example 6
The preparation method of the tetragonal phase nano-doped zirconia ceramic powder material with the particle size D50 of less than 100nm comprises the following specific steps:
(1) dissolving a certain amount of zirconium salt precursor n-butyl alcohol zirconium, doping element-containing lanthanum nitrate and surfactant polyether into a mixed solvent of water and organic alcohol isopropanol (the volume ratio of water to organic alcohol is 1:0.5), mechanically stirring to obtain a clear solution, and recording the clear solution as a solution A.
(2) A quantity of oxalate ammonium hydrogen oxalate was weighed and dissolved in a volume of deionized water solution and designated as solution B. The mass ratio of the zirconium salt precursor to the oxalate is 1.5: 1;
(3) and (2) uniformly mixing the solution A and the solution B by adopting a peristaltic pump in a forward addition, reverse addition or parallel flow mode respectively, reacting at room temperature, wherein the concentration of a zirconium salt precursor in a formed reaction system is 10 wt%, the mass percentage content of doped elements is 5 wt%, then continuously stirring for 2 days to obtain a white gel solution, and centrifugally separating to obtain a white precipitate product, wherein the centrifugal speed of the centrifugal separation is 12000rpm, and the centrifugal time is 5min each time. Washing with water, drying at 60 ℃, roasting at 600 ℃ for 5h, and finally performing gas-state grinding treatment on the obtained solid powder sample to obtain the tetragonal-phase nano-doped zirconia ceramic powder material with the granularity D50 smaller than 100 nm. The selected equipment for gaseous grinding treatment of the solid powder sample is an airflow pulverizer, the power is 4KW, the powder product is collected through a cyclone separator, the power of an air compressor is 50KW, and 1.0Mpa compressed air is provided for pulverization.
Claims (1)
1. A tetragonal phase nano-doped zirconia ceramic powder material is characterized by being prepared by the following steps:
dissolving 10g of zirconium oxychloride, 0.1g of yttrium nitrate and 1.0g of PEG-10000 by using 500ml of a mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 1: 0.1; stirring for half an hour, adding 400ml of aqueous solution containing 10g of ammonium oxalate into the solution through a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at the rotating speed of 11000rpm for 5 minutes to obtain white gel, then washing the white gel product twice with water and ethanol respectively, drying the white gel product in the air at 60 ℃ for 12 hours, calcining the white gel product at 1000 ℃ for 4 hours, treating the calcined gel product through a gaseous pulverizer with the gas pressure of 1.0MPa, and collecting the obtained powder sample through a cyclone separator to obtain the tetragonal-phase doped nano-zirconia ceramic powder with the D50 of 90 nm.
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