CN109704759A - A kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof - Google Patents
A kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 59
- -1 compound rare-earth modified zirconia Chemical class 0.000 title claims abstract description 58
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 52
- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 55
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 33
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005119 centrifugation Methods 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 16
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 16
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 16
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical class [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims 1
- 239000001923 methylcellulose Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 72
- 235000011114 ammonium hydroxide Nutrition 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 238000009283 thermal hydrolysis Methods 0.000 description 13
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 10
- 229910009523 YCl3 Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000003801 milling Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 7
- 230000006698 induction Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 239000011224 oxide ceramic Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910003317 GdCl3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910018057 ScCl3 Inorganic materials 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 229910009454 Y(OH)3 Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000006070 nanosuspension Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of compound rare-earth modified zirconia ceramic powder and preparation method thereof, the preparation method includes the following steps: that the mixed liquor by zirconates, rare-earth salts, dispersing agent is heated to 25 DEG C -90 DEG C, and ammonium hydroxide is added thereto or acid solution adjusts H+Concentration to 0.1-5mol/L；H will be adjusted+Solution heating after concentration carries out hydro-thermal reaction, and 90 DEG C are cooled to after reaction hereinafter, obtaining hydrous zirconium oxide(HZO) suspension；It is still aging after pH to alkalinity to adjust that ammonium hydroxide is added into the hydrous zirconium oxide(HZO) suspension；Mixed liquor is centrifuged, washed, dried, is calcined, by calcined powder and deionized water, dispersant uniformly after ball milling, slurry is obtained, then slurry is subjected to fine gtinding, centrifugation, washing and drying, obtains nano composite rare earth modified zirconia ceramic powder.Method provided by the invention solves and consumes a large amount of ethylene glycol and polyvinyl alcohol organic matter in existing method, and the reluctant technical problem of organic wastewater generated.
Description
Technical field
The present invention relates to technical field of powdered material preparation, make pottery more particularly, to a kind of compound rare-earth modified zirconia
Porcelain powder and preparation method thereof.
Background technique
Zirconium oxide is a kind of highly important structural material, rear-earth-doped stabilizing zirconia, especially doped yttrium Stable Oxygen
Change zirconium, there are the characteristics such as good lower thermal conductivity, strength and toughness, low elastic modulus, high thermal shock resistance, elevated operating temperature, answer extensively
For fields such as national defence, weaving, the energy and aerospaces, in various metal oxide ceramics, the importance of zirconium oxide is only secondary
In aluminium oxide ceramics.It is exactly its " brittleness " that pure zirconia ceramics, which have a deadly defect, i.e., because of the volume that phase transformation generates
Expansion causes it with poor fracture toughness.
Patent Office of the People's Republic of China disclose a kind of superfine powder as raw material of high-performance zirconium oxide ceramics and preparation process (application number:
CN02115615.8), superfine powder as raw material of high-performance zirconium oxide ceramics and preparation process, be related to it is a kind of prepare high-performance zirconia pottery
The raw material and preparation process of the Ultramicro-powder of ceramic products.Superfine powder as raw material is to add aluminium oxide Ultramicro-powder in zirconium oxide, oxidation yttrium powder.
Preparation process be by zirconyl chloride solution, yttria solution mix be made into zirconia powder mother liquor, in mother liquor be added ethylene glycol and
Polyvinyl alcohol water solution is uniformly mixed, then it is reacted with ammonium bicarbonate soln, react the precipitating of generation through drainage, drying, forge
Burn to obtain high-performance zirconium oxide ceramics Ultramicro-powder.But the patent can consume a large amount of ethylene glycol and polyvinyl alcohol organic matter, generate
Organic wastewater be difficult to handle, while this invent essence be chemical coprecipitation, have the shortcomings that the shared of coprecipitation, system
Standby powder can generate extremely serious reunion, and agglomeration traits can seriously affect the application of micro-nano powder.
Summary of the invention
Based on this, the present invention provides one kind by hydro-thermal hydrolyze and spatial induction precipitating cladding rare earth mode prepare it is compound
The method of rare earth modified zirconia ceramics powder solves a large amount of ethylene glycol of above-mentioned consumption and polyvinyl alcohol organic matter, and generates
The reluctant technical problem of organic wastewater.
One kind is hydrolyzed by hydro-thermal and spatial induction precipitating cladding rare earth mode prepares the modified oxidized zircon ceramic of compound rare-earth
The method of powder, includes the following steps:
(1) mixed liquor of zirconates, rare-earth salts, dispersing agent is heated to 25 DEG C -90 DEG C, ammonium hydroxide or acid solution tune is added thereto
Save H+Concentration to 0.1-5mol/L；
(2) H will be adjusted+The solution heating of concentration carries out hydro-thermal reaction, and 90 DEG C are cooled to after fully reacting hereinafter, obtaining water
Close zirconia nanosuspensions；
(3) in Xiang Suoshu hydrous zirconium oxide(HZO) suspension be added ammonium hydroxide come adjust pH to basic surface coat rare earth after stand it is old
Change；
(4) treated that solution is centrifuged by step (3), washs, dries, calcining, by calcined powder and go from
Sub- water, dispersant uniformly after ball milling, obtain slurry, by slurry grinding, centrifugation, washing and dry, it is multiple to obtain nanometer
Close rare earth modified zirconia ceramics powder.
In one of the embodiments, the zirconates in step (1) include zirconium oxychloride, zirconium chloride, zirconium nitrate and
One of zirconium sulfate is a variety of, preferably zirconium oxychloride；The rare-earth salts include chlorate, nitrate and sulfate one kind or
It is a variety of, the preferably salt-mixture of cerium chloride and yttrium chloride；The acid solution includes one of hydrochloric acid, nitric acid and sulfuric acid or a variety of,
Preferably hydrochloric acid；The dispersing agent includes one of hydroxypropyl methyl cellulose, hydroxypropyl cellulose and polyethylene glycol or more
Kind.
The Zr in the zirconates in step (1) in one of the embodiments,4+Concentration be 0.1-2.5mol/L, Zr4 +With Y in yttrium salt3+Molar concentration rate be 99:2-90:20, Zr4+Molar ratio with metal ion in other rare-earth salts is 99:1-
92:8, dispersant concentration are 0.5~5g/L.
The mixed liquor in step (1) is mixed in one of the embodiments, with the revolving speed of 300-1000r/min,
The speed that ammonium hydroxide or acid solution are added is 1-10000mL/min, wherein the concentration of ammonium hydroxide is 0.5-6mol/L, and the concentration of acid solution is
0.1-3mol/L。
120 DEG C -300 DEG C are warming up in step (2) in one of the embodiments, the time of hydro-thermal reaction is 3-
20h。
In one of the embodiments, in the step (3) temperature be 25 DEG C -90 DEG C, mixing speed 300-
Under conditions of 1000r/min, ammonium hydroxide is added into the hydrous zirconium oxide(HZO) suspension with the speed of 5-5000mL/min to adjust
PH to 8-14.
It is centrifuged in the step (4), washed, dried, in calcination processing in one of the embodiments, it is described dry
Dry temperature is 50-80 DEG C, drying time 10-14h；The calcination temperature is 800-1200 DEG C, calcination time 1-3h.
The revolving speed of the ball milling in step (4) is 30-90r/min, time 6- in one of the embodiments,
12h；The revolving speed of grinding is 2000-4000r/min, charging rate 20-100mL/min, time 30-120min；Described point
Powder includes including acid polyethylene ammonium, Macrogol 6000 or dodecyl sodium sulfate, and the mass percent that dispersing agent is added is
0.1%-0.5%.
When the slurry in step (4) grinds, is centrifuged, washing and is dry in one of the embodiments, slurry is solid
Content is 10%-30%, and material ball ratio 1:5-1:15, the temperature of the drying is 50-80 DEG C, and the dry time is 10-14h.
The present invention also provides a kind of compound rare-earth modified zirconia ceramic powder, the compound rare-earth modified zirconia ceramic powders
It is made up of above-mentioned preparation method.
The present invention is largely divided into reaction solution preparation, the heavy yttrium technique of hydro-thermal hydrolysis process, spatial induction, the heavy cerium of spatial induction
Five technique, aftertreatment technology steps.In reaction solution process for preparation, by the way that ammonium hydroxide or acid solution solution is added, make in solution
Part Zr4+Hydrolysis obtains nucleus, the amount of ammonium hydroxide or acid solution is added to control the forming amount of nucleus by control, and then play control
The effect of nano zircite partial size, the reaction equation which is related to have:
ZrOCl2+H2O→ZrO2·nH2O+2HCl
NH3·H2O+HCl→NH4Cl+H2O
It sinks in rare earth element craft in spatial induction, mainly progress surface coats rare earth element, which is to pass through table
The mode of face induced precipitation cladding carries out rear-earth-doped, can control nano zircite by adjusting the additive amount of rare earth element
Crystal phase composition.And the doping way is easy to operate, and uniform doping is easy to industrialized production, the reaction equation which is related to
Have:
YCl3+3NH3·H2O→Y(OH)3+3NH4Cl
Me3++3NH3·H2O→Me(OH)3+3NH4+
The technological operation is simple, at low cost, has synthetic powder partial size small relative to traditional ball milling mixing technique, will not
Impurity is introduced, and the uniform component of nanoscale can be reached.
In aftertreatment technology, rare earth modified zirconium oxide precursor is calcined at high temperature, removes residual moisture and is occurred
It reacts below:
ZrO2·nH2O→ZrO2+nH2O
2Y(OH)3→Y2O3+3H2O
2Me(OH)3→Me2O3+3H2O
It also occur that the solid solution process of rare earth oxide, obtains the modified oxidized zircon ceramic of nano rare earth in calcination process
Powder；Some agglomerations can be generated by being difficult to avoid that in calcination process, therefore twice ball milling process has also been devised in the present invention, passes through before this
Common corase grinding, then it is finer ground can eliminate reunion, obtain the rare earth modified zirconia ceramics powder of mono-dispersed nano.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram disclosed by the invention for preparing compound rare-earth modified zirconia powder；
Rare earth modified zirconia ceramics powder TEM figure made from method disclosed in Fig. 2,3 present invention implementations 1；
Fig. 4 is rare earth modified zirconia ceramics powder XRD diagram made from method disclosed in embodiment 1.
Fig. 5 is rare earth modified zirconia ceramics powder XRD diagram made from method disclosed in embodiment 2.
Fig. 6 is rare earth modified zirconia ceramics powder XRD diagram made from method disclosed in embodiment 3.
Fig. 7 is rare earth modified zirconia ceramics powder XRD diagram made from method disclosed in embodiment 4.
Fig. 8 is rare earth modified zirconia ceramics powder XRD diagram made from method disclosed in embodiment 5.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
It is a kind of to coat the side that rare earth mode prepares rare earth modified zirconium oxide composite granule by hydro-thermal hydrolysis and spatial induction
Method, the preparation method the following steps are included:
(1) zirconium oxychloride, rare-earth salts, dispersing agent material solution, Zr reaction solution preparation method: are prepared4+Concentration 0.1~
2.5mol/L, Zr4+With Y3+Molar concentration ratio is 99:2~90:20, Zr4+It is 99 with other rare earth element molar concentration ratios:
1~92:8, dispersant concentration are 0.5~5g/L；Material solution is placed in reaction kettle, in 25~90 DEG C of temperature, high-speed stirred
Under the conditions of 300~1000r/min, concentration is added with 1~10000mL/min as 0.5~6mol/L ammonia spirit by atomizer
Or 0.1~3mol/L hydrochloric acid solution adjusts material solution H+Concentration, so that Zr in solution4+Partial hydrolysis generates nucleus, adjusts molten
Liquid H+Concentration is 0.1~5mol/L to control hydrolysis generation nucleus amount to get hydro-thermal hydrolysis solution；
(2) hydro-thermal hydrolysis process: reaction solution obtained by step (1) is transferred to teflon lined stainless steel and is contrary
It answers in kettle, is warming up to 120~300 DEG C of progress 6~20h of hydro-thermal reaction, crystal grain is grown up on the basis of nucleus during the reaction,
It obtains spherical hydrous zirconia particles, after the completion of hydro-thermal reaction, takes out hydrothermal reaction kettle and be cooled to 90 DEG C hereinafter, obtaining
Hydrous zirconium oxide(HZO) suspension；
(3) the heavy rare earth element craft of spatial induction: by hydrous zirconium oxide(HZO) suspension obtained by step (2), in temperature 25~90
DEG C, under the conditions of 300~10000r/min of high-speed stirred, 0.5~6mol/L ammonium hydroxide is added with 5~5000mL/min by atomizer
Solution makes rare earth element, in the surface of hydrous zirconium oxide(HZO), make hydrous zirconium oxide(HZO) suspension pH value with hydroxide form homogeneous precipitation
It is 8~14, until heavy rare earth element precipitating is completely, static ageing 6~for 24 hours；
(4) aftertreatment technology: solution is centrifuged, washs to be placed in baking oven at 50~80 DEG C and dry 10~14h,
1~3h is calcined at 800~1200 DEG C.Powder, deionized water, dispersing agent press solid content: 10%~30%, pellet matter after calcining
Measure ratio: 1:5~1:15, dispersing agent: 0.1%~0.5% (percentage of powder quality) is uniformly mixed, and general milling machine is in revolving speed
6~12h of ball milling obtains uniformly mixed slurry under 30~90r/min, then through fine grinding machine in 2000~4000r/ of revolving speed
After grinding 30~120min under the conditions of min, 20~100mL/min of charging rate, pulp centrifuged alcohol is washed 1~3 time, 50~80
Dry 10~14h obtains compound rare-earth modified zirconia ceramic powder at DEG C.
In order to clearly illustrate the present invention, following embodiment is enumerated.
Embodiment 1
(1) ZrOCl is prepared2、YCl3、Ce(NO3)3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Ce3+Mole
Than for 95.05:1.45:3.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, pass through addition
The H of 5.95mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.6mol/L, H+Concentration is
1.5mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3 +It uniformly is deposited in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, is hydrated oxygen after obtaining heavy yttrium/cerium
Change zirconium suspension；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, is by solid content by powder, deionized water, acid polyethylene ammonium after calcining
30%, pellet mass ratio is 1:10, acid polyethylene ammonium is that 0.1% (percentage of powder quality) is uniformly mixed, general milling machine
6~12h of ball milling obtains uniformly mixed slurry at revolving speed 60r/min, then through fine grinding machine revolving speed 3000r/min, into
After grinding 60min under the conditions of material speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth at 75 DEG C
Modified zirconia ceramic powder.
Embodiment 2
(1) ZrOCl is prepared2、YCl3、Ce(NO3)3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Ce3+Mole
Than for 94.57:1.93:3.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, pass through addition
The H of 5.95mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.6mol/L, H+Concentration is
1.2mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 160 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3+It is uniform heavy
It forms sediment in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, obtains heavy yttrium/cerium rear suspension liquid；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, is by solid content by powder, deionized water, acid polyethylene ammonium after calcining
30%, pellet mass ratio is 1:10, acid polyethylene ammonium is that 0.1% (percentage of powder quality) is uniformly mixed, general milling machine
6~12h of ball milling obtains uniformly mixed slurry at revolving speed 60r/min, then through fine grinding machine revolving speed 3000r/min, into
After grinding 60min under the conditions of material speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth at 75 DEG C
Modified zirconia ceramic powder.
Embodiment 3
(1) ZrOCl is prepared2、YCl3、Ce(NO3)3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Ce3+Molar ratio
For 94.09:2.41:3.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 2.8mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.0mol/L, H+Concentration is
1.2mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 160 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3+It is uniform heavy
It forms sediment in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, obtains heavy cerium/magnesium rear suspension liquid；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, and powder, deionized water, acid polyethylene ammonium after calcining are pressed solid content:
30%, pellet mass ratio: 1:10, acid polyethylene ammonium: 0.1% (percentage of powder quality) is uniformly mixed, and general milling machine exists
6~12h of ball milling obtains uniformly mixed slurry under revolving speed 60r/min, then through fine grinding machine in revolving speed 3000r/min, charging
After grinding 60min under the conditions of speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth and changes at 75 DEG C
Property zirconia ceramics powder.
Embodiment 4
(1) Zr (NO is prepared3)4、Y(NO3)3、CeCl3Hydroxypropyl methyl cellulose mixed solution, wherein Zr4+:Y3+:Ce3+It rubs
Material solution is placed in reaction kettle than being 93.6:2.9:3.5, under 60 DEG C of water-baths, 500r/min stirring, passes through addition by you
The H of 2.1mol/L dilute nitric acid solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is
1.8mol/L, hydroxypropyl methyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 160 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3+It is uniform heavy
It forms sediment in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, obtains heavy yttrium/cerium rear suspension liquid；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, centrifugation is washed 3 times, then with ethanol washing 2 times
Afterwards, 10h at 75 DEG C in an oven, calcines 2h at 1000 DEG C after grinding, by powder, deionized water, polyethylene glycol after calcining
6000 press solid content: 30%, pellet mass ratio: 1:10, Macrogol 6000: 0.1% (percentage of powder quality) mixing is equal
Even, general milling machine 6~12h of ball milling at revolving speed 60r/min obtains uniformly mixed slurry, then through fine grinding machine in revolving speed
After grinding 60min under the conditions of 3000r/min, charging rate 50mL/min, pulp centrifuged alcohol is washed 2 times, the dry 10h at 75 DEG C
Obtain compound rare-earth modified zirconia ceramic powder.
Embodiment 5
(1) ZrCl is prepared4、YCl3、CeCl3, polyethylene glycol mixed solution, wherein Zr4+:Y3+:Ce3+Molar ratio is
Material solution is placed in reaction kettle by 89.775:4.725:5.5, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 2.1mol/L dilute hydrochloric acid solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is
1.8mol/L, Polyethylene glycol are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 160 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3+It is uniform heavy
It forms sediment in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, obtains heavy yttrium/cerium rear suspension liquid；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, by powder after calcining, deionized water, dodecyl sodium sulfate by containing admittedly
Amount: 30%, pellet mass ratio: 1:10, dodecyl sodium sulfate: 0.1% (percentage of powder quality) is uniformly mixed, common ball
Grinding machine 6~12h of ball milling at revolving speed 60r/min obtains uniformly mixed slurry, then through fine grinding machine in revolving speed 3000r/
After grinding 60min under the conditions of min, charging rate 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h is answered at 75 DEG C
Close rare earth modified zirconia ceramics powder.
Embodiment 6
(1) Zr (SO is prepared4)2、YCl3、CeCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Ce3+Molar ratio
For 92.25:2.25:5.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 1.05mol/L dilution heat of sulfuric acid adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=0.6mol/L, H+Concentration is
1.8mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 160 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Ce3+It is uniform heavy
It forms sediment in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, obtains heavy yttrium/cerium rear suspension liquid；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, and powder, deionized water, acid polyethylene ammonium after calcining are pressed solid content:
30%, pellet mass ratio: 1:10, acid polyethylene ammonium: 0.1% (percentage of powder quality) is uniformly mixed, and general milling machine exists
6~12h of ball milling obtains uniformly mixed slurry under revolving speed 60r/min, then through fine grinding machine in revolving speed 3000r/min, charging
After grinding 60min under the conditions of speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth and changes at 75 DEG C
Property zirconia ceramics powder.
Embodiment 7
(1) ZrOCl is prepared2、YCl3、ScCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Sc3+Molar ratio
For 92.25:2.25:5.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 5.95mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.6mol/L, H+Concentration is
1.5mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Sc3 +It uniformly is deposited in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, is hydrated oxygen after obtaining heavy yttrium/scandium
Change zirconium suspension；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, is by solid content by powder, deionized water, acid polyethylene ammonium after calcining
30%, pellet mass ratio is 1:10, acid polyethylene ammonium is that 0.1% (percentage of powder quality) is uniformly mixed, general milling machine
6~12h of ball milling obtains uniformly mixed slurry at revolving speed 60r/min, then through fine grinding machine revolving speed 3000r/min, into
After grinding 60min under the conditions of material speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth at 75 DEG C
Modified zirconia ceramic powder.
Embodiment 8
(1) ZrOCl is prepared2、YCl3、NdCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Nd3+Molar ratio
For 92.25:2.25:5.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 5.95mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.6mol/L, H+Concentration is
1.5mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Nd3 +It uniformly is deposited in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, is hydrated oxygen after obtaining heavy yttrium/neodymium
Change zirconium suspension；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, is by solid content by powder, deionized water, acid polyethylene ammonium after calcining
30%, pellet mass ratio is 1:10, acid polyethylene ammonium is that 0.1% (percentage of powder quality) is uniformly mixed, general milling machine
6~12h of ball milling obtains uniformly mixed slurry at revolving speed 60r/min, then through fine grinding machine revolving speed 3000r/min, into
After grinding 60min under the conditions of material speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth at 75 DEG C
Modified zirconia ceramic powder.
Embodiment 9
(1) ZrOCl is prepared2、YCl3、GdCl3, hydroxypropyl cellulose mixed solution, wherein Zr4+:Y3+:Gd3+Molar ratio
For 92.25:2.25:5.5, material solution is placed in reaction kettle, under 60 DEG C of water-baths, 500r/min stirring, passes through addition
The H of 5.95mol/L dilute ammonia solution adjusting end reaction solution+Concentration makes the final C of solutionZr 4+=1.6mol/L, H+Concentration is
1.5mol/L, hydroxypropyl cellulose concentration are 0.5g/L to get hydro-thermal reaction solution；
(2) step (1) acquired solution is transferred in the stainless steel cauldron of teflon lined, is heated to 180 DEG C
Hydro-thermal hydrolysis is carried out, cooling obtains hydrous zirconium oxide(HZO) suspension after reaction 12h；
(3) by hydrous zirconium oxide(HZO) suspension at 60 DEG C, 500r/min, 10% ammonium hydroxide, which is added, with 10mL/min makes Y3+/Gd3 +It uniformly is deposited in hydrous zirconia particles surface, when pH of suspension=9 stopping addition ammonium hydroxide, is hydrated oxygen after obtaining heavy yttrium/gadolinium
Change zirconium suspension；
(4) by step (3) the still aging 12h of suspension, centrifugation washing 3 times, then with after ethanol washing 2 times, in an oven
10h at 75 DEG C calcines 2h at 1000 DEG C after grinding, is by solid content by powder, deionized water, acid polyethylene ammonium after calcining
30%, pellet mass ratio is 1:10, acid polyethylene ammonium is that 0.1% (percentage of powder quality) is uniformly mixed, general milling machine
6~12h of ball milling obtains uniformly mixed slurry at revolving speed 60r/min, then through fine grinding machine revolving speed 3000r/min, into
After grinding 60min under the conditions of material speed 50mL/min, pulp centrifuged alcohol is washed 2 times, dry 10h obtains compound rare-earth at 75 DEG C
Modified zirconia ceramic powder.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of compound rare-earth modified zirconia ceramic powder, which comprises the steps of:
(1) mixed liquor of zirconates, rare-earth salts and dispersing agent is heated to 25 DEG C -90 DEG C, ammonium hydroxide is added thereto or acid solution adjusts H+
Concentration to 0.1-5mol/L；
(2) H will be adjusted+Solution heating after concentration carries out hydro-thermal reaction, and 90 DEG C are cooled to after reaction hereinafter, obtaining aqua oxidation
Zirconium suspension；
(3) it is still aging after pH to alkalinity to adjust that ammonium hydroxide is added in Xiang Suoshu hydrous zirconium oxide(HZO) suspension；
(4) treated that solution is centrifuged by step (3), washs, dries, calcining, by calcined powder and deionized water,
Dispersant uniformly after ball milling, obtain slurry, then by slurry grinding, centrifugation, washing and dry, obtain nano combined dilute
Land reform zirconia ceramics powder.
2. preparation method according to claim 1, which is characterized in that in step (1), the zirconates includes oxychlorination
One of zirconium, zirconium chloride, zirconium nitrate and zirconium sulfate are a variety of, preferably zirconium oxychloride；The rare-earth salts be mainly chlorate,
One or more, the preferably salt-mixture of cerium chloride and yttrium chloride of nitrate and sulfate；The dispersing agent includes hydroxypropyl
One of methylcellulose, hydroxypropyl cellulose and polyethylene glycol are a variety of；The acid solution includes in hydrochloric acid, nitric acid and sulfuric acid
One or more, preferably hydrochloric acid.
3. preparation method according to claim 1, which is characterized in that in step (1), Zr in the zirconates4+Concentration
For 0.1-2.5mol/L, Zr4+With Y in yttrium salt3+Molar concentration rate be 99:2-90:20, Zr4+With the molar ratio of other rare-earth salts
For 99:1-92:8, dispersant concentration is 0.5~5g/L.
4. preparation method according to claim 1, which is characterized in that in step (1), the mixed liquor is with 300-
The revolving speed of 1000r/min mixes, and the speed of ammonium hydroxide or acid solution addition is 1-10000mL/min, wherein the concentration of ammonium hydroxide is 0.5-
6mol/L, the concentration of acid solution are 0.1-3mol/L.
5. preparation method according to claim 1, which is characterized in that in step (2), be warming up to 120 DEG C -300 DEG C, water
The time of thermal response is 3-20h.
6. preparation method according to claim 1, which is characterized in that be 25 DEG C -90 in temperature in the step (3)
DEG C, under conditions of mixing speed is 300-1000r/min, with the speed of 5-5000mL/min to the hydrous zirconium oxide(HZO) suspension
The middle ammonium hydroxide that 0.5-6mol/L is added adjusts pH to 8-14.
7. preparation method according to claim 1, which is characterized in that be centrifuged in step (4), washed, dried, calcined
In processing, the drying temperature is 50-80 DEG C, drying time 10-14h；The calcination temperature is 800-1200 DEG C, when calcining
Between be 1-3h.
8. preparation method according to claim 1, which is characterized in that in step (4), the revolving speed of the ball milling is 30-
90r/min, time 6-12h；The revolving speed of fine gtinding be 2000-4000r/min, charging rate 20-100mL/min, when
Between be 30-120min；The dispersing agent includes acid polyethylene ammonium, Macrogol 6000 or dodecyl sodium sulfate, and dispersing agent adds
The mass percent entered is 0.1%-0.5%.
9. preparation method according to claim 1, which is characterized in that the grinding of the slurry in step (4), centrifugation,
When washing and drying, slurry solid content is 10%-30%, material ball ratio 1:5-1:15；The temperature of the drying is 50-80 DEG C,
The dry time is 10-14h.
10. compound rare-earth modified zirconia ceramic powder made from preparation method as described in any one of claim 1 to 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925732A (en) * | 2020-08-17 | 2020-11-13 | 湖南皓志科技股份有限公司 | Preparation method of nano neodymium oxide coated zirconia powder |
| CN112266244A (en) * | 2020-10-14 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of high-sintering-activity zirconium oxide powder |
| CN114551910A (en) * | 2022-02-25 | 2022-05-27 | 内蒙古科技大学 | Composite rare earth oxide and preparation method and application thereof |
| CN116102350A (en) * | 2022-12-27 | 2023-05-12 | 中铝广西有色稀土开发有限公司 | Preparation method of spherical composite zirconia powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102743978A (en) * | 2012-07-12 | 2012-10-24 | 三达膜科技（厦门）有限公司 | Method for preparing modified zirconia ceramic ultrafiltration membrane via yttrium doping |
-
2019
- 2019-03-15 CN CN201910196919.5A patent/CN109704759A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102743978A (en) * | 2012-07-12 | 2012-10-24 | 三达膜科技（厦门）有限公司 | Method for preparing modified zirconia ceramic ultrafiltration membrane via yttrium doping |
Non-Patent Citations (5)
| Title |
|---|
| 刘志宏等: "钇稳定四方相氧化锆粉末的水热水解法制备", 《中国有色金属学报》 * |
| 尹邦跃: "《陶瓷核燃料工艺》", 31 January 2016, 哈尔滨工程大学出版社 * |
| 朱鸿民: "《冶金研究 2008年》", 31 March 2008, 冶金工业出版社 * |
| 李清等: "《工程材料及机械制造基础》", 30 June 2016, 华中科技大学出版社 * |
| 顾大明等: "《功能材料制备实验》", 30 June 2011, 哈尔滨工业大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925732A (en) * | 2020-08-17 | 2020-11-13 | 湖南皓志科技股份有限公司 | Preparation method of nano neodymium oxide coated zirconia powder |
| CN111925732B (en) * | 2020-08-17 | 2021-09-21 | 湖南皓志科技股份有限公司 | Preparation method of nano neodymium oxide coated zirconia powder |
| CN112266244A (en) * | 2020-10-14 | 2021-01-26 | 安徽元琛环保科技股份有限公司 | Preparation method of high-sintering-activity zirconium oxide powder |
| CN114551910A (en) * | 2022-02-25 | 2022-05-27 | 内蒙古科技大学 | Composite rare earth oxide and preparation method and application thereof |
| CN114551910B (en) * | 2022-02-25 | 2023-09-22 | 内蒙古科技大学 | Composite rare earth oxide and preparation method and application thereof |
| CN116102350A (en) * | 2022-12-27 | 2023-05-12 | 中铝广西有色稀土开发有限公司 | Preparation method of spherical composite zirconia powder |
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Application publication date: 20190503 |