CN114014651A - Method for producing nano composite zirconia powder by hydrothermal method - Google Patents
Method for producing nano composite zirconia powder by hydrothermal method Download PDFInfo
- Publication number
- CN114014651A CN114014651A CN202111066618.4A CN202111066618A CN114014651A CN 114014651 A CN114014651 A CN 114014651A CN 202111066618 A CN202111066618 A CN 202111066618A CN 114014651 A CN114014651 A CN 114014651A
- Authority
- CN
- China
- Prior art keywords
- zirconium
- yttrium
- powder
- hydrothermal
- zirconia
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000000843 powder Substances 0.000 title claims abstract description 122
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000227 grinding Methods 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 238000005469 granulation Methods 0.000 claims abstract description 15
- 230000003179 granulation Effects 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000889 atomisation Methods 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 62
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 57
- 239000012065 filter cake Substances 0.000 claims description 42
- 239000002131 composite material Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 28
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical group CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 20
- 238000005086 pumping Methods 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 16
- 238000004537 pulping Methods 0.000 claims description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910021512 zirconium (IV) hydroxide Inorganic materials 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
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 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 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims description 2
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 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
- 238000010902 jet-milling Methods 0.000 claims 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims 1
- 238000011085 pressure filtration Methods 0.000 claims 1
- 238000004448 titration Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 description 31
- 238000000034 method Methods 0.000 description 28
- 238000003825 pressing Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 20
- 239000013078 crystal Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000005054 agglomeration Methods 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000003801 milling Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 10
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 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 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000001 dental powder Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 206010002198 Anaphylactic reaction Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical group [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 241001417518 Rachycentridae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910009454 Y(OH)3 Inorganic materials 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 229910006220 ZrO(OH)2 Inorganic materials 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 210000004489 deciduous teeth Anatomy 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 208000030194 mouth disease Diseases 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 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 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- FVPMPWKTWOILGX-UHFFFAOYSA-G yttrium(3+);zirconium(4+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Y+3].[Zr+4] FVPMPWKTWOILGX-UHFFFAOYSA-G 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- -1 zirconium oxygen ions Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C04B35/488—Composites
-
- 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
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method for producing high-end nano composite zirconia powder for dentistry, oxygen sensitive elements and the like by a hydrothermal method, belonging to the field of novel functional ceramic materials. By changing the preparation process, the amorphous precipitate can form an effective crystallization mechanism without specific hydrothermal precursor organic treatment. The invention comprises the following steps: dissolving zirconium and yttrium soluble salt in water, filtering, alkalizing, washing, hydrothermal treatment, atomization drying, calcining, grinding, surface modification, granulation, packaging and the like. The invention adopts advanced low-cost differential hydrothermal process treatment, so that the product completely meets the manufacturing requirements of the dental field, and replaces similar products of Tosoh corporation of Japan; the proportion of zirconium and yttrium and the calcining temperature are changed, the granulated powder is degummed at low temperature, and the natural powder which is used for manufacturing the electronic ceramic-oxygen sensor and is less than 300 nanometers is obtained by air flow grinding.
Description
Technical Field
The invention belongs to the field of dental and electronic ceramic new materials, and particularly relates to a method for producing nano composite zirconia powder by a hydrothermal method.
Background
Under the background of the aging of the global population, oral diseases become important factors influencing the life quality of people, and the phenomena of gum allergy and metal microleakage are easy to occur on the existing ceramic teeth which are subject to being held because of the metal crown bottom. The flexural strength of the zirconia false tooth is approximately three times higher than that of the porcelain tooth, the hardness is about two times of that of the porcelain tooth, the chewing resistance is strong, the zirconia false tooth is insoluble in saliva and acid-base food, adverse reaction and anaphylactic reaction do not exist, cytotoxicity does not exist, and the zirconia false tooth is regarded as a twin brother of a primary tooth by the medical community, so that the zirconia full-porcelain restoration has wide application prospect in the medical field; with the progress of society and the development of science and technology, the sensors with various position functions such as flow, positioning, gas concentration, speed, light brightness, humidity, distance and the like are added to the earliest sensors for water temperature and pressure. The oxygen sensor of the electronic fuel injection engine has the main functions of regulating and controlling the air-fuel ratio through signal transmission feedback, reducing the environmental pollution caused by the emission of automobile exhaust and improving the fuel combustion quality of the automobile engine, and has great significance in advocating energy conservation and emission reduction to the climate change.
Because the zirconia false tooth has a warm and moist jade-like high-imitation appearance, excellent mechanical property and high biocompatibility, and an oxygen sensor with complex use working conditions is a ceramic element which is irreplaceable in daily life of people, the zirconia false tooth has wide use range, large market capacity and high manufacturing precision, the powder quality of the 'Wan pottery source' is required to be new, and the main inorganic additive for enhancing the heat resistance of the diaphragm in the zirconia powder and the ceramic product is hydrothermal nano zirconia ultramicro powder. The method has the advantages that the method has smooth raw materials in China, mature novel manufacturing equipment and alternate appearance in new and old markets, and the novel process is utilized to produce the novel material, in particular the environment-friendly and zero-emission novel energy lithium battery anode coating material and the solid electrolyte (lithium lanthanum zirconium oxygen is abbreviated as LLZO), so that the method has wide development prospect.
At present, most of the domestic zirconium oxide powder production processes are zirconium oxychloride doped yttrium chloride, and the zirconium oxychloride doped yttrium chloride is subjected to dissolution, filtration, ammonia water precipitation, filter pressing and washing, filter cake high-temperature calcination, grinding, glue adding granulation, sieving, mixing and packaging, and the processes are collectively called coprecipitation processes in the industry, and have the defects of a plurality of crystal lattices, high porosity in the crystal and serious crystal grain agglomeration. Even in a preferred state, when the obtained zirconia powder is used for ceramic manufacture, the sintered density is small, the ceramic crystal grain is large, the bending strength is low, the energy density is low, and the light transmittance is poor.
Disclosure of Invention
The invention provides a method for producing nano composite zirconia powder by a hydrothermal method, which can form an effective crystallization mechanism without specific organic treatment of a hydrothermal precursor by changing the preparation process, completes the nucleation-growth-crystallization-elusive microscopic process, reduces the unit energy consumption of the finished product by 20 percent compared with the unit energy consumption of the finished product, and increases the yield by 3 percent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
(1) mixing soluble salts of zirconium and yttrium, wherein the ratio of the soluble salts of zirconium and yttrium is converted into the mass ratio of oxides: 91.2 percent or 94.2 percent of zirconium oxide and the balance of corresponding yttrium oxide, wherein the mass ratio of the mixture to water is 1:1, the mixture is dissolved by adding water, the mixture is stirred for half an hour, filtered and titrated with ammonia water simultaneously, the pH value of the instantaneous reaction is controlled to be 8.5-9.5, a fixed filter pressing-washing mode is set, and four rounds of washing are carried out to obtain an ammonia precipitation hydroxide filter cake; the chemical reactions involved in this section are as follows:
ZrOCl2+2NH3﹒H2O——ZrO(OH)2↓+2NH4Cl
YCl3+3NH3﹒H2O——Y(OH)3↓+3NH4Cl；
the wet method for producing the composite zirconia has the history that the quantitative production in China is less than twenty years, and belongs to a novel material which has no substitution and is necessary in the market. In the existing technology, zirconium oxychloride (calculated as zirconium oxide) is doped with 5.4% yttrium oxide and 0.25% aluminum oxide (both yttrium and aluminum are mixed with zirconium oxygen ions in the form of soluble salt), and then dissolved in water, filtered, and co-titrated with ammonia water to produce amorphous hydrated hydroxide precipitate. The procedure selects undoped alumina, and the proportion of zirconium and yttrium is different from that of the traditional coprecipitation process;
(2) adding water into the filter cake obtained in the step (1) according to the mass ratio of 1:1.5, simultaneously adding triethanolamine which is converted into 3-4% of zirconia according to the mass ratio, putting the mixture into a titanium reaction kettle, stirring the mixture at the rotating speed of 1200rpm for 40 minutes for pulping, adjusting the rotating speed to 80rpm, carrying out hydrothermal treatment at the temperature rising rate of 2 ℃/min to 135 ℃ and 145 ℃, keeping the kettle pressure at 0.25-0.45MPa for 16-32 hours, cooling, carrying out filter pressing, washing to obtain the yttrium-doped hydrous zirconia filter cake,
in the hydrated zirconia slurry subjected to hydrothermal treatment, zirconium oxygen atoms are nucleated in situ by virtue of an O-Zr-O bond, the hydrated zirconia slurry slowly grows at the hydrothermal temperature, the zirconium and oxygen atoms in crystal lattices are arranged in regular periodic change, the intra-crystal porosity is low, the impurity content is low, the crystal purity and the self-forming degree are high, unaluted chloride ions are only simply adsorbed on a filter cake and are easily washed to the ppm level, and adjacent particles are reduced due to Cl-The pulling of the slurry forms salt bridge agglomeration, and a filter cake formed by the slurry is slightly soluble in strong acid and aqua regia; the existing process does not set up a hydrothermal procedure, the obtained hydrous zirconium yttrium hydroxide belongs to amorphous precipitation, is easy to dissolve in strong acid and aqua regia, atoms forming a matrix form a disordered aggregation state, and wraps impurities, and the washing equilibrium concentration of chloride ions is up to 300 ppm;
(3) adding water into the hydrous zirconia filter cake obtained in the step (2) according to the mass ratio of 1:1.5 to the water, stirring at the rotating speed of 1200rpm for 1 hour to prepare pulp, pumping the pulp into a drying tower, adjusting the inlet temperature of the drying tower to be 220-;
the working section adopts a mode of carrying out low-temperature flash evaporation dehydration by atomization drying, reduces the agglomeration of liquid bridges, leads dry powder to be in a natural loose state, increases the distance between adjacent particles, is convenient for high-temperature calcination and reduces the agglomeration of oxygen bridges.
In the prior art, an atomization drying mode is not set for low-temperature rapid dehydration, when the high-temperature calcination is carried out, a plurality of adjacent particles are strained by the residual adsorbed water in a filter cake due to surface tension, crystal lattices in crystals are deformed and overlapped, and liquid bridge and oxygen bridge agglomeration are easily formed, so that hard agglomeration is formed among the particles, and the subsequent grinding dispersion and ceramic sintering are not facilitated;
(4) calcining the dried powder obtained in the step (3) at high temperature, and setting a push plate speed for the material to stay in a high-temperature area for 2-3 hours to obtain nano composite zirconia powder with high characteristic softness, crystallization degree, monodispersion degree, powder activity and thermal stability;
the intermediate of the existing calcining process is a filter cake with serious agglomeration degree, and because the filter cake contains a large amount of structural water and absorbed water, high-concentration liquid bridge agglomeration is easily formed under the action of water molecules; the dehydrated amorphous filter cake has more surface atom proportion, large energy and close contact, and the crystal lattice is disorderly expanded at high temperature, so that oxygen bridge agglomeration is easily formed;
(5) adding water into the composite zirconia calcined powder obtained in the step (4) according to the mass ratio of 1:1, grinding at the speed of 600rpm, grinding balls of zirconia with the diameter of 0.3mm, controlling the median particle size of the slurry to be 250 nanometers of 220-;
high dispersion is one of the important indexes of powder. The process is characterized in that the 'three-bridge' control for causing powder agglomeration is adopted, so that the calcined powder forming pseudo-agglomeration is easily broken up in the grinding and pulping working section to form monodisperse ultrafine particles, and the slurry has high fluidity and uniform stability;
the same calcining temperature and heat preservation time of the prior art, the same solid content of 50 percent, grinding to 500 nanometers, viscosity thickening and extremely poor fluidity of slurry, and even blockage of a pump pipe can cause that the process can not be propelled;
(6) changing the doped yttrium oxide of the step (1) to 5 mol and the doped zirconium oxide of the step (1) to 95 mol, preserving the heat of the granulation powder obtained in the step (5) for 2 hours at 380 ℃, cooling and carrying out gas milling, adjusting the vibration frequency of a feeding machine to be 1500 times/min, and adjusting the pressure of the gas milling to be 0.80MPa, so as to obtain natural powder which is not agglomerated and is less than 300 nanometers in long-term stability;
the natural powder less than 300 nanometers is not obtained simply by grinding, and the natural powder is needed to be paved by hydrothermal treatment, so that the ultramicro powder with high crystallization degree and high monodispersion degree can be obtained, and then the ultramicro powder with the stable period more than 1 year can be obtained by actual surface modification; the common non-hydrothermal method powder, the proper hydrothermal temperature and heat preservation time are not set, the proper surface modification and degumming temperature are not matched, even if the composite zirconia powder less than 300 nanometers is obtained by sand grinding and air flow grinding, the composite zirconia powder can not be in a natural loose state for a long time, the high energy is generated by lattice defects, the mutual aggregation is reduced, the internal energy is in a low-energy stable state, and the particle size of the powder is secondarily grown.
In the above step, when the ratio of the soluble salts of zirconium and yttrium is converted into the mass ratio of oxides: when the zirconium oxide is 94.2 percent and the yttrium oxide is 5.8 percent, the high-temperature calcination temperature in the step (4) is 1030-1040 ℃, the granulated powder obtained in the step (5) passes through a 100-mesh screen, and undersize is taken to obtain finished granulated powder;
when the ratio of the soluble salt of zirconium and yttrium is converted into mass ratio of oxide: when the zirconium oxide accounts for 91.2 percent and the yttrium oxide accounts for 8.8 percent, the high-temperature calcination temperature in the step (4) is 1140-1150 ℃;
in the step (1), the zirconium soluble salt is zirconium oxychloride, zirconium nitrate, zirconium sulfate or zirconium tetrachloride, the yttrium soluble salt is yttrium chloride, yttrium nitrate or yttrium sulfate, the alkali is 10% sodium hydroxide solution or 8% ammonia water, and the zirconium oxychloride and the yttrium chloride are preferably used as raw materials and 8% ammonia water is preferably used as a zirconium yttrium precipitator in the application; the dissolving and stirring speed of the zirconium-yttrium mixed salt is 1200 rpm; in the process, the water is deionized water; the fixed filter pressing washing mode is as follows: and (3) filter cake: stirring for 40 minutes with the water mass ratio of 1:4, the stirring rotating speed of 1200rpm, the air pressure pressed into the plate and frame filter of 0.40MPa, and the type of the filter cloth of 750B; except for special description, all the mixture ratios of the materials are mass ratios; zirconium oxychloride and yttrium chloride solutionThe mass ratio of the mixed solution to water is measured by taking the mass data of zirconium oxychloride as a measurement basis; all particle sizes are mean particle sizes: calcining powder in the step (4), granulating powder in the step (5), primary grain size (also called lattice spacing and referred to as primary grain size in the industry) of natural powder with the grain size smaller than 300 nanometers in the step (6), grinding grain size (referred to as secondary grain size in the industry) of composite zirconia slurry in the step (5), grain size of the granulating powder and grain size (referred to as tertiary grain size in the industry) of natural powder with the grain size smaller than 300 nanometers in the step (6); the mass ratio of 5 mol of yttria to 95 mol of zirconia was 8.8% in terms of yttria and 91.2% in terms of zirconia; the zirconia described in this application is actually hafnium zirconia in total, with hafnium oxide accounting for about 1.8%, as is zirconium oxychloride, with a 5Y (abbreviation for 5 moles of yttrium oxide) zirconia content of 91.2%, including hafnium oxide, as is the case with all zirconias referred to in the text; the dental powder mixture of 5.8% yttria and 94.2% zirconia is customarily classified into 3 mol yttria, 3Y-ZrO for short2(ii) a The particle size of the 5Y composite zirconia for the natural powder with the particle size of less than 300 nanometers cannot be changed in a large range through the gas pressure and the gas milling frequency of the jet mill, the main process is required to be used as a bedding, the jet mill simply breaks up soft agglomerates formed by low-temperature degumming of granulated powder to reduce the original parameters, the particle size range of the jet mill is generally between 260-290 nanometers, the data is not balanced and controllable in the jet mill section, the data is related to the main process and is an essential value, the relation between the air pressure and the gas milling frequency is very small and can be ignored, the data is particularly provided, and the specific parameters of less than 300 nanometers are not used as control values to be expressed in the embodiment;
the 'organic treatment' in the '… specific hydrothermal precursor organic treatment' in the abstract content of the specification means that zirconium oxalate, zirconium acetate or other organic zirconium with low cost performance is used as a raw material, or zirconium oxychloride is used as a raw material to perform chemical reaction before hydrothermal, and the transformation form of the organic zirconium appears in the process, so that the manufacturing cost and the organic salt recovery difficulty are increased, which is one of the reasons for the low cost of the invention described in the application, because the organic zirconium is transformed from the zirconium oxychloride, and the zirconium oxychloride is the basic raw material with the highest cost performance of zirconium salt;
in the abstract of the specification, the step (6) in the claim 1 and the step (6) in the specification (the same applies before and after) refer to that the granulated powder is degummed at the low temperature of 380 ℃, wherein the glue refers to the sum of all organic matters added in grinding and pulping, and the industry is conventionally called glue, and the supplementary description is provided.
Has the advantages that: the invention provides a method for producing nano composite zirconia powder by a hydrothermal method, which adopts an advanced hydrothermal method production process, emphasizes the completeness of powder nucleation, growth and development, ensures consistent crystal grains and reduces the agglomeration of salt bridges, liquid bridges, oxygen bridges and other three bridges, and forms a dental and electrical functional ceramic new material with high crystallization degree, less intragranular impurities, low pores, high monodispersion degree, good sintering activity, high product hardness, high bending strength and high light transmittance; the monodispersion degree of the powder particles is high, the powder particles are uniformly mixed, and all components are in atomic distance contact; the process parameters are reasonably established, the original grain size (primary grain diameter) is in a quasi-nanometer state, the macroscopic size of the 5Y electronic ceramic powder is below 300 nanometers, and the process is most suitable for the process of forming small thin or special-shaped electronic ceramics such as an oxygen sensor by a flow-extension method, and is initiated at home.
The composite zirconia powder produced by the effective hydrothermal method is applied to the fields of biomedical materials including dental materials and oxygen sensors, lithium battery anode coating, solid electrolyte, intelligent wearing, electronic communication, sky and sea areas and other high-tip fine-end fields, and the performance of downstream products is greatly improved.
Drawings
FIG. 1 and FIG. 2 are TEM images of the composite zirconia powder obtained in the examples of the present invention;
FIGS. 3 and 4 are XRD patterns of the composite zirconia powder obtained in the example of the invention;
FIGS. 5 and 6 are particle size distribution diagrams of the composite zirconia slurry after polishing obtained in the example of the present invention;
FIG. 7 is a particle size distribution diagram of a natural powder of less than 300 nm obtained by low-temperature degumming and air milling of 5Y granulated powder in the embodiment of the invention
FIG. 8 is a graph showing the desorption of the composite zirconia powder obtained in the examples of the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
example 1
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 54.5Kg of yttrium chloride solution (containing 14.65 percent of yttria), putting the zirconium oxychloride and 54.5Kg of yttrium chloride solution into a dissolving kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, simultaneously dripping the zirconium oxychloride and 8 percent ammonia water into another reaction kettle, controlling the pH value of the reaction to be 8.5 under the stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing the mixture into a plate frame by using 0.40MPa of air, filtering, adding water into a filter cake 1:1.5, stirring for 40 minutes, pressing the mixture into the plate frame by using 0.40MPa of air, filtering, washing and filter-pressing for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into the zirconium oxide and has the mass ratio of 3 percent, stirring for 1 hour to prepare slurry, pumping the slurry into a titanium reaction kettle, heating the slurry to 135 ℃ at the speed of 2 ℃/min, keeping the kettle pressure to 0.25MPa, cooling, pressing and washing for multiple times according to the washing mode, until the chloride ion of the filtrate is less than 5ppm, adding water into the filter cake after the hydrothermal process, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 220 ℃, controlling an outlet temperature by using a feeding flow rate, atomizing and drying at 90 ℃, placing the hydrothermal drying powder into a sagger, staying for 3 hours in a high-temperature region at 1030 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with the diameter of 0.3mm, controlling the median particle size to be 220 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyoyo grease Co., Ltd, adding polyethylene glycol with the mass ratio of 100:0.8 and the molecular weight of 400, carrying out surface modification at the mass ratio of 100:2.5, controlling the rotating speed to be 120rpm, stirring for 1 hour, setting the inlet temperature of a granulating tower at 200 ℃, controlling the outlet temperature at 90 ℃ by using the feeding flow rate and the frequency of an atomizing disc at 42HZ, carrying out spray granulation, sieving the granulated powder with a 100-mesh sieve, taking the undersize product, mixing, and packaging to obtain the finished granulated powder.
Example 2
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 54.5Kg of yttrium chloride solution (containing 14.65 percent of yttria), putting the zirconium oxychloride and 54.5Kg of yttrium chloride solution into a dissolving kettle containing 360Kg of pure water, stirring the zirconium oxychloride and the zirconium oxychloride for 30 minutes, filtering the zirconium oxychloride, simultaneously dripping the zirconium oxychloride and 8 percent of ammonia water into another reaction kettle, controlling the pH value of the reaction to be 9.5 under the stirring state, aging and stirring the zirconium oxychloride and the zirconium oxychloride for 40 minutes after the reaction is finished, pressing the zirconium oxychloride into the plate-frame filter by 0.40MPa of air, adding water into the filter cake 1:1.5, stirring the triethanolamine with the proportion of 4 percent of the zirconium oxide for 1 hour to prepare pulp, pumping the pulp into a titanium reaction kettle, raising the temperature at the speed of 2 ℃/min to 145 ℃, keeping the kettle pressure at 0.45MPa for 16 hours, cooling, pressing and washing the filtrate for multiple times according to the washing mode until the chloride ion of the filtrate is less than 5ppm, adding water into the filter cake 1:1.5 after the hydrothermal reaction, stirring, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 240 ℃, controlling an outlet temperature with a feeding flow rate to be 100 ℃ for atomization drying, placing the hydrothermal drying powder into a sagger to stay in a 1040 ℃ high-temperature area for 2 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling a median particle size to be 250 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyoyo grease Co., Ltd., a mass ratio of 100:1.2, adding polyethylene glycol with a molecular weight of 400, a mass ratio of 100:1.5, carrying out surface modification, controlling a rotation speed of 120rpm, stirring for 1 hour, setting an inlet temperature of a granulating tower at 220 ℃, controlling an outlet temperature at 105 ℃ with a feeding flow rate and a frequency of an atomizing disc at 42HZ, carrying out spray granulation, sieving the granulated powder with a 100-mesh sieve, taking the undersize product, mixing, and packaging to obtain the finished granulated powder.
Example 3
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 54.5Kg of yttrium chloride solution (containing 14.65 percent of yttria), putting the zirconium oxychloride and 54.5Kg of yttrium chloride solution into a dissolving kettle containing 360Kg of pure water, stirring the zirconium oxychloride and the zirconium oxide for 30 minutes, filtering the zirconium oxychloride and the yttrium chloride, simultaneously dripping the zirconium oxychloride and the 8 percent of ammonia water into another reaction kettle, controlling the pH value of the reaction to be 9.0 under the stirring state, aging and stirring the zirconium oxychloride and the yttrium chloride after the reaction is finished for 40 minutes after the reaction is finished, pressing the zirconium oxychloride and the zirconium oxide into the plate and frame for filtering by using 0.40MPa of air, adding water into the filter cake 1:1.5, stirring the water and the water for pulping the filter cake 1:4, stirring the water for 40 minutes, pressing the water into the plate and frame for filtering the filter by using 0.40MPa of air, washing and pressing and filtering the filter press for four times, cooling the filter cake, and washing the filtrate by multiple times according to the washing mode until the chloride ion of the filter cake is less than 5ppm after the hydrothermal treatment, adding water into the filter cake 1:1.5, adding water and filtering the filtrate, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 230 ℃, controlling an outlet temperature with a feeding flow rate to be atomized and dried at 95 ℃, placing the hydrothermal dried powder into a sagger to stay in a 1035 ℃ high temperature area for 2.5 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling the median particle size to be 230 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyowa grease Co., Ltd, adding polyethylene glycol with a mass ratio of 100:1.0 and a molecular weight of 400, modifying the surface at a mass ratio of 100:2.0, stirring at 120rpm for 1 hour, setting up an inlet temperature of a granulation tower at 210 ℃, controlling an outlet temperature at 95 ℃ with a feeding flow rate and an atomizing disc frequency at 42HZ, and performing spray granulation, sieving the granulated powder with a 100-mesh sieve, taking the undersize product, mixing, and packaging to obtain the finished granulated powder.
Example 4
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 85.4.5Kg of yttrium chloride solution (containing 14.65 percent of yttria), putting the zirconium oxychloride and 85.4.5Kg of yttrium chloride solution into a dissolving kettle containing 360Kg of pure water, stirring the zirconium oxychloride and the zirconium oxychloride for 30 minutes, filtering the zirconium oxychloride, simultaneously dripping the zirconium oxychloride and 8 percent of ammonia water into another reaction kettle, controlling the pH value of the reaction to be 8.5 under the stirring state, aging and stirring the zirconium oxychloride and the zirconium oxychloride for 40 minutes after the reaction is finished, pressing the zirconium oxychloride into the plate frame by using 0.40MPa of air, filtering the zirconium oxychloride into a filter cake 1:4 by adding water, stirring the water for 40 minutes, pressing the water into the plate frame by using 0.40MPa of air, washing and filter-pressing the zirconium oxychloride for four times, stirring the water and the triethanolamine which is folded into 3 percent of the mass ratio of the zirconium oxide for 1 hour to prepare slurry, pumping the titanium reaction kettle, heating the zirconium oxychloride at the speed of 2 ℃/min to 135 ℃ and the kettle pressure of 0.25MPa, keeping the kettle pressure for 32 hours, cooling, pressing and washing the zirconium oxychloride filtrate for multiple times according to obtain the filtrate until the filtrate with the above washing mode, adding water, and filtering the filter cake 1:1.5 by adding water, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 220 ℃, controlling an outlet temperature by using a feeding flow rate, atomizing and drying at 90 ℃, placing the hydrothermal drying powder into a sagger, staying at a 1140 ℃ high temperature region for 3 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with the diameter of 0.3mm, controlling the median particle size to be 220 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyoyo grease Co., Ltd., the mass ratio of 100:0.8, adding polyethylene glycol with the molecular weight of 400, the mass ratio of 100:2.5, carrying out surface modification, controlling the rotation speed to be 120rpm, stirring for 1 hour, setting the inlet temperature of a granulating tower to be 200 ℃, controlling the outlet temperature to be 90 ℃ by using the feeding flow rate, controlling the frequency of an atomizing disc to be 42HZ, carrying out spray granulation, drying the granulated powder at 380 ℃, preserving heat for 2 hours, cooling, carrying out air milling, and adjusting the vibration frequency of a feeding machine to be 1500 times/min and the air milling pressure to be 0.80MPa to obtain another finished product of the composite zirconia natural powder with the particle size less than 300 nanometers.
Example 5
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 85.4Kg of yttrium chloride solution (containing 14.65 percent of yttria), putting the zirconium oxychloride and 85.4Kg of yttrium chloride solution into a dissolving kettle containing 360Kg of pure water, stirring the zirconium oxychloride and the zirconium oxychloride for 30 minutes, filtering the zirconium oxychloride, simultaneously dripping the zirconium oxychloride and 8 percent of ammonia water into another reaction kettle, controlling the pH value of the reaction to be 9.5 under the stirring state, aging and stirring the zirconium oxychloride and the zirconium oxychloride for 40 minutes after the reaction is finished, pressing the zirconium oxychloride into the plate-frame filter by 0.40MPa of air, adding water into the filter cake 1:1.5, stirring the triethanolamine with the zirconium oxide proportion of 4 percent, pulping the mixture for 1 hour, pumping the mixture into a titanium reaction kettle, heating the zirconium oxychloride at the speed of 2 ℃/min to 145 ℃ and the kettle pressure of 0.45MPa, keeping the kettle pressure for 16 hours, cooling, and performing multiple times of pressure filtration-washing according to the washing mode until the chloride ion of the filtrate is less than 5ppm, adding water into the filter cake 1:1.5 after the hydrothermal reaction, stirring the water, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 240 ℃, controlling an outlet temperature with a feeding flow rate to be 100 ℃ for atomization drying, placing the hydrothermal drying powder into a sagger to stay in a high-temperature zone at 1150 ℃ for 2 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with the diameter of 0.3mm, controlling the median particle size to be 250 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyoyo grease Co., Ltd, adding polyethylene glycol with the molecular weight of 100:1.2 and the molecular weight of 400, carrying out surface modification at the mass ratio of 100:1.5, controlling the rotating speed to be 120rpm, stirring for 1 hour, setting the inlet temperature of a granulating tower at 220 ℃, controlling the outlet temperature at 105 ℃ with the feeding flow rate and the frequency of an atomizing disc at 42HZ, carrying out spray granulation, drying the granulated powder at 380 ℃, preserving heat for 2 hours, cooling, carrying out air milling, and adjusting the vibration frequency of a feeding machine to be 1500 times/min and the air milling pressure to be 0.80MPa to obtain another finished product of the composite zirconia natural powder with the particle size less than 300 nanometers.
Example 6
A method for producing nano composite zirconia powder by a hydrothermal method comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (containing 36 percent of zirconia) and 85.4Kg of yttrium chloride solution (containing 14.65 percent of yttria) into a dissolving kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, simultaneously dripping the solution and 8 percent of ammonia water into another reaction kettle, controlling the pH value of the reaction to be 9.0 under the stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing the solution into a plate frame by using 0.40MPa of air for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing the filter cake into the plate frame by using 0.40MPa of air for filtering, washing and filter-pressing for four times, adding water into the filter cake 1:1.5, adding triethanolamine with the proportion of 3.5 percent of zirconia, stirring for 1 hour for pulping, pumping into a titanium reaction kettle, raising the temperature to 137 ℃ at the speed of 2 ℃/min, keeping the kettle pressure for 0.37MPa of hydrothermal reaction, cooling, pressing, filtering and washing the filter cake 1:1.5 and adding water after the hydrothermal reaction until the chloride ion of the filtrate is less than 5ppm, Stirring at 1200rpm for 1 hour for pulping, pumping into a drying tower, designing an inlet temperature of 230 ℃, controlling an outlet temperature with a feeding flow rate to be atomized and dried at 95 ℃, placing the hydrothermal dried powder into a sagger to stay in a high-temperature zone at 1145 ℃ for 2.5 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder 1:1, grinding at 600rpm in a nano-grinder, grinding with a zirconia grinding ball with the diameter of 0.3mm, controlling the median particle size to be 230 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 sold by Nippon Kyowa grease Co., Ltd, adding polyethylene glycol with the mass ratio of 100:1.0 and the molecular weight of 400, modifying the surface, stirring at 120rpm for 1 hour, setting the inlet temperature of a granulation tower at 210 ℃, controlling the outlet temperature at 95 ℃ with the feeding flow rate and the frequency of an atomizing disc at 42HZ, and performing spray granulation, drying the granulated powder at 380 ℃, preserving heat for 2 hours, cooling, carrying out air milling, and adjusting the vibration frequency of a feeding machine to be 1500 times/min and the air milling pressure to be 0.80MPa to obtain another finished product of the composite zirconia natural powder with the particle size less than 300 nanometers.
The washing water related to the step 1) and the step 2) can be reused in a rotary mode, namely the last washing water after hydrothermal is used for washing the fourth filter cake before hydrothermal, the last filter cake after hydrothermal is backwashed, the third filter cake before hydrothermal is washed, the third washing backwater before hydrothermal is used as the washing water for reacting the first filter cake, and the fourth backwater before hydrothermal is used as the washing water for reacting the second filter cake. Then evaporating the high-concentration washing water by a triple-effect evaporator, recovering ammonium chloride, and reusing the condensate as high-purity water to enter a production line. This procedure is not within the scope of the subject technology invention of this application and is outlined here.
The obtained product was subjected to characterization tests, and the results were as follows:
FIGS. 1 and 2 are TEM images of the composite zirconia obtained in example 6 of example 3, respectively, from which it can be seen that the mean sizes of the primary crystals of the powder are 50nm and 40 nm, respectively;
FIGS. 3 and 4 are X-ray diffraction patterns of the composite zirconia powders obtained in examples 1 to 3 and 4 to 6, respectively, and it can be seen from the patterns that the crystal phase of the powder in FIG. 3 is 94% of tetragonal phase and 6% of monoclinic phase; FIG. 4 shows the 100% tetragonal phase;
fig. 5 and 6 are particle size distribution diagrams after slurrying and grinding of calcined powder in example 3 and example 6, respectively, and the average particle sizes are 230 nm and 240 nm, respectively, and it can be seen from the diagrams that the particle size distribution of the slurry is very narrow;
FIG. 7 is a particle size distribution diagram of the natural powder of example 6 with particle size less than 300 nm after 13 months of storage, the average particle size is 270 nm without agglomeration, and it can be seen from the figure that the particle size distribution of the powder is very narrow;
FIGS. 8-1 and 8-2 are graphs showing desorption curves of the composite zirconia powders obtained in examples 3 and 6 of the present invention, respectively, and it can be seen from these graphs that 8-1 is the specific surface area of the granulated powder of the product of example 3 of 10.33m2The peak 8-2 is that the specific surface area of the natural powder body of less than 300 nanometers of the embodiment 6 is 10.44m2/g。
TABLE 1 comparison of the product of the invention with the customer-supplied same product characterization
0.25% Al is doped in Nippon cobia powder2O3。
TABLE 2 comparison of the test data of the false teeth sintered by customers of the product of the present invention and similar products with the national standard
No specific requirements are provided for light transmission (light transmittance), Rockwell hardness and sintering density in national standard GB 30367-2013/ISO 6872: 2008.
TABLE 3 comparison of the product of the invention with the customer-supplied same product characterization
Table 4 shows the comparison of the test data of the sensor sintered by the customer between the product of the present invention and the similar product
In tables 1 and 3, 3Y-ZrO2Dental powder and 5Y-ZrO2The characteristics of the sensor powder are shown in tables 2 and 4, which are parameter comparisons after the ceramic is sintered by customers, and it can be seen visually from tables 2 and 4 that the product of the invention has similar performance with the similar product in Japan, and the 5Y electrical property is higher than that in Japan.
To facilitate understanding of the electrical property test parameters of table 4, test conditions and data are provided as follows:
sensor combustion test electrical property output characteristic
1) Detection conditions are as follows:
gas: combustion gas
Exhaust temperature: 350-400 deg.C
And (3) exhausting environment: dense (λ ═ 0.972 ± 0.004) dilute (λ ═ 1.024 ± 0.004)
2) Measurement items
And (3) outputting a rich combustion voltage: output Voltage (VR) in dense state gas
Output of lean burn voltage: output voltage in lean gas (VL)
Response time: (concentrated to dilute): output 600 ═ 300mV desired Time (TRL)
Response time: (dilute to concentrated): output 300 ═ 600mV required Time (TLR)
Sensor nernst cell internal resistance: rin
And (4) conclusion:
1. the signal jump amplitude (VR-VL) is 860-36mV, DKK is 920-69mV, and the same ratio values are respectively 60 and 33 lower;
2. the TRL value is 70ms, the DKK is 93ms, and the time is shorter and more stable;
3. the TLR value is 89ms, DKK is 100ms, and the time is more stable;
4. the product of the invention has lower internal resistance and better sensing element activity.
The powder of the invention contains manganese oxide, iron oxide, nickel oxide, cobalt oxide, magnesium oxide, titanium oxide, chromium oxide, aluminum oxide, barium titanate and binary or multi-component composition thereof, and the powder can improve the crystallinity, the dispersibility, the uniformity, the sintering property and the stability, and simultaneously can ensure that the energy density, the safety, the periodicity, the weather resistance, the long-term effect and the mechanical property of domestic electronic components and other functional ceramics are greatly improved, which is a fact that the industry recognizes no conflict. Many domestic electronic component manufacturing enterprises such as thermosensitive, photosensitive, sound-sensitive, pressure-sensitive, humidity-sensitive, magnetic-sensitive, capacitor, filter and the like still use a physical mechanical mixing method at present, then obtain 0.5 micron powder by grinding, obtain high-quality powder without considering crystal nucleation, crystal lattice development and anti-agglomeration treatment, and still realize the original and laggard cognition before 25 years: namely, the inertial introduction of the purity of powder is a few nine, and the crystal spacing is a few nanometers, and the descriptions are frequently found in industrial meetings of powder-ceramic-battery-electronics and the like.
It needs to be added that when the content of yttrium oxide reaches 4.0 mol, the light transmittance of the powder after being made into porcelain can be improved by the process of the invention to reach more than 46%; when the content of the yttrium oxide is increased to 5.0 mol, or other auxiliary agents are doped, the main processes such as hydrothermal conditions, surface modification formula and the like are not changed, and the variety of the 300 nanometer composite zirconium oxide natural powder can be diversified, which is a consensus in the industry and can be obtained without creative labor.
For the understanding of the present application, the above-mentioned examples are only given to help the understanding of the present application and should not be construed as limiting the adjustment of the parameters within the process critical range of the present application. The scope of the invention according to the present application is not limited to the combination of the above-described features, and also covers other combinations of the above-described features or equivalent features in any combination without departing from the scope of the invention. The technical solutions formed by mutually replacing the above features with (but not limited to) technical features having similar functions disclosed in this application are within the scope of this application, and it will be appreciated by those skilled in the art that other relevant figures and corresponding process flows can be obtained from these figures without creative efforts, and the performance of the product of the present invention can be obtained by the production process as well as the performance similar or similar to that of the product of the present invention, which is also supplemented herein.
Claims (10)
1. A method for producing nano composite zirconia powder by a hydrothermal method is characterized by comprising the following steps:
(1) mixing soluble salts of zirconium and yttrium, wherein the ratio of the soluble salts of zirconium and yttrium is converted into the mass ratio of oxides: 91.2 percent or 94.2 percent of zirconium oxide and the balance of corresponding yttrium oxide, adding water to dissolve zirconium yttrium mixed salt and water according to the mass ratio of 1:1, filtering, titrating with alkaline water simultaneously, adjusting the pH value of the instantaneous reaction of zirconium yttrium solution and alkaline water flow control to be 8.5-9.5, setting up a fixed filter pressing-washing mode, and washing for four times to obtain an alkaline precipitation hydroxide filter cake;
(2) adding water into the filter cake obtained in the step (1) according to the mass ratio of 1:1.5, simultaneously adding triethanolamine which is converted into 3-4% of the mass ratio of zirconia, stirring for 40 minutes for pulping, heating to 135-145 ℃ at the speed of 2 ℃/min for hydrothermal treatment under the pressure of 0.25-0.45MPa, keeping for 16-32 hours, cooling, performing pressure filtration, and washing to obtain an yttrium-doped hydrous zirconia filter cake;
(3) adding water into the yttrium-doped hydrous zirconia filter cake obtained in the step (2) according to the mass ratio of 1:1.5, stirring for 1 hour for pulping, and drying at low temperature to obtain natural fluffy dried powder;
(4) calcining the dried powder obtained in the step (3) at high temperature, and staying in a high-temperature area for 2-3 hours to obtain nano composite zirconia calcined powder;
(5) adding water into the composite zirconia calcined powder obtained in the step (4) according to the mass ratio of 1:1, grinding to control slurry, grinding the median particle size to 220-plus 250 nm to obtain composite zirconia slurry, pumping the slurry into a storage tank with stirring, adding modified polyacrylic acid D-305 and polyethylene glycol with the molecular weight of 400 for surface modification, stirring for 1 hour, and then performing spray granulation to obtain granulated powder;
(6) and (3) preserving the heat of the granulated powder obtained in the step (5) at 380 ℃ for 2 hours, cooling to room temperature, carrying out jet milling, and adjusting the vibration frequency of a feeding machine to be 1500 times/min and the pressure of the jet milling to be 0.80MPa to obtain loose powder with the particle size of less than 300 nanometers.
2. The hydrothermal process of claim 1, wherein when the ratio of the soluble salts of zirconium and yttrium is converted to an oxide mass ratio: when the zirconium oxide is 94.2 percent and the yttrium oxide is 5.8 percent, the high-temperature calcination temperature in the step (4) is 1030-1040 ℃, the granulated powder obtained in the step (5) passes through a 100-mesh screen, and the undersize product is taken to obtain the finished granulated powder.
3. The hydrothermal process of claim 1, wherein when the ratio of the soluble salts of zirconium and yttrium is converted to an oxide mass ratio: when the zirconium oxide is 91.2 percent and the yttrium oxide is 8.8 percent, the high-temperature calcination temperature of the step (4) is 1140-1150 ℃.
4. The hydrothermal process of claim 1, wherein in step (1) the zirconium-soluble salt is zirconium oxychloride, zirconium nitrate, zirconium sulfate, or zirconium tetrachloride, and the yttrium-soluble salt is yttrium chloride, yttrium nitrate, or yttrium sulfate; the alkali is 10% sodium hydroxide solution or 8% ammonia water; mixing the zirconium and yttrium soluble salts, adding water to dissolve the zirconium and yttrium soluble salts, stirring at the speed of 1200rpm, and stirring for 40 minutes; the model of the filter cloth is 750B; after titration with alkali, the stirring speed was 600rpm and the stirring was carried out for 40 minutes.
5. The hydrothermal process for producing a nanocomposite zirconia powder of claim 1 or 4, wherein in step (1), the zirconium-soluble salt is zirconium oxychloride, the yttrium-soluble salt is yttrium chloride, and the alkali is 8% ammonia water.
6. The hydrothermal method for producing nano-composite zirconia powder according to claim 1, wherein the water-adding pulping stirring of the filter cake and the washing stirring speed of the filter cake after hydrothermal in step (2) are both 1200rpm, and the stirring speed after the slurry is transferred into the hydrothermal kettle is 80 rpm.
7. The hydrothermal method for producing the nano-composite zirconia powder according to claim 1, wherein the stirring speed of the water-added pulping of the filter cake in the step (3) is 1200 rpm; drying by adopting a mode of low-temperature dehydration by adopting atomization drying.
8. The hydrothermal method for producing nano-composite zirconia powder of claim 7, wherein the low-temperature drying specifically comprises the steps of: pumping the slurry into a drying tower from a storage tank, wherein the inlet temperature of the drying tower is 220-240 ℃, the flow rate of the slurry is adjusted, the outlet temperature is controlled to be 90-100 ℃, the stirring speed of the slurry in the storage tank is 120 r/min, and the rotation frequency of an atomizing disc is 45 HZ.
9. The hydrothermal method for producing a nanocomposite zirconia powder according to claim 1, wherein in the step (5), the mass ratio of the modified polyacrylic acid type D-305 to the zirconia is 100:0.8-1.2, and the mass ratio of the polyethylene glycol 400 to the zirconia is 100: 1.5-2.5; the stirring speed was 300 rpm.
10. The hydrothermal process for producing a nanocomposite zirconia powder of claim 1, wherein the spray granulation in step (5) comprises the following steps: setting the inlet temperature of the granulation tower at 200-220 ℃, the stirring speed of the slurry in the storage tank at 120rpm, controlling the outlet temperature at 90-105 ℃ by using the feeding flow rate, and the rotation frequency of the atomizing disc at 42HZ, and carrying out spray granulation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066618.4A CN114014651B (en) | 2021-09-10 | 2021-09-10 | Method for producing nano composite zirconia powder by hydrothermal method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066618.4A CN114014651B (en) | 2021-09-10 | 2021-09-10 | Method for producing nano composite zirconia powder by hydrothermal method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114014651A true CN114014651A (en) | 2022-02-08 |
| CN114014651B CN114014651B (en) | 2023-10-24 |
Family
ID=80054233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111066618.4A Active CN114014651B (en) | 2021-09-10 | 2021-09-10 | Method for producing nano composite zirconia powder by hydrothermal method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114014651B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521142A (en) * | 2022-10-09 | 2022-12-27 | 中国科学院赣江创新研究院 | Rare earth doped hafnium oxide nano powder and preparation method and application thereof |
| CN116161958A (en) * | 2022-12-27 | 2023-05-26 | 中铝广西有色稀土开发有限公司 | Preparation method of yttrium-stabilized zirconia nano-powder |
| CN116354716A (en) * | 2023-04-06 | 2023-06-30 | 南京金鲤新材料有限公司 | Preparation process of zirconia powder with high sintering activity and low specific surface area |
| CN117228715A (en) * | 2023-11-10 | 2023-12-15 | 琥崧科技集团股份有限公司 | Preparation method of zirconium dioxide sintered body |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113254A1 (en) * | 2001-12-17 | 2003-06-19 | Vladimir Belov | Method for manufacturing stabilized zirconia |
| US20050175525A1 (en) * | 2004-02-06 | 2005-08-11 | Millennium Inorganic Chemicals, Inc. | Nano-structured particles with high thermal stability |
| CN1757605A (en) * | 2005-11-03 | 2006-04-12 | 山东大学 | Method for preparing nanometer zirconium oxide for thermal barrier coating |
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN102267813A (en) * | 2010-06-01 | 2011-12-07 | 上海景文材料科技发展有限公司 | Hydrothermal precipitation method production process for nanometer thulium-zirconium ceramic powder |
| CN104086175A (en) * | 2014-07-23 | 2014-10-08 | 西安航天复合材料研究所 | Preparation method of YSZ ceramic powder for plasma spraying |
| CN108467264A (en) * | 2018-03-06 | 2018-08-31 | 三祥新材股份有限公司 | A kind of combined oxidation zirconium powder for lambda sensor |
| CN108609651A (en) * | 2018-06-13 | 2018-10-02 | 宣城晶瑞新材料有限公司 | A kind of preparation of novel nano zirconia material |
| CN108640677A (en) * | 2018-06-22 | 2018-10-12 | 万华化学集团股份有限公司 | A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable |
| US20200369573A1 (en) * | 2017-07-31 | 2020-11-26 | Kuraray Noritake Dental Inc. | Method for producing zirconia particle-containing powder |
| CN112811903A (en) * | 2021-01-12 | 2021-05-18 | 浙江金琨锆业有限公司 | Remove Cl in zirconia powder-Method (2) |
| CN113200567A (en) * | 2021-05-26 | 2021-08-03 | 先导薄膜材料有限公司 | High-sintering-activity zirconium oxide powder and preparation method thereof |
-
2021
- 2021-09-10 CN CN202111066618.4A patent/CN114014651B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030113254A1 (en) * | 2001-12-17 | 2003-06-19 | Vladimir Belov | Method for manufacturing stabilized zirconia |
| US20050175525A1 (en) * | 2004-02-06 | 2005-08-11 | Millennium Inorganic Chemicals, Inc. | Nano-structured particles with high thermal stability |
| CN1757605A (en) * | 2005-11-03 | 2006-04-12 | 山东大学 | Method for preparing nanometer zirconium oxide for thermal barrier coating |
| CN101613123A (en) * | 2009-08-05 | 2009-12-30 | 邢长生 | The hydrothermal synthesis method of IVB family metal oxide |
| CN102267813A (en) * | 2010-06-01 | 2011-12-07 | 上海景文材料科技发展有限公司 | Hydrothermal precipitation method production process for nanometer thulium-zirconium ceramic powder |
| CN104086175A (en) * | 2014-07-23 | 2014-10-08 | 西安航天复合材料研究所 | Preparation method of YSZ ceramic powder for plasma spraying |
| US20200369573A1 (en) * | 2017-07-31 | 2020-11-26 | Kuraray Noritake Dental Inc. | Method for producing zirconia particle-containing powder |
| CN108467264A (en) * | 2018-03-06 | 2018-08-31 | 三祥新材股份有限公司 | A kind of combined oxidation zirconium powder for lambda sensor |
| CN108609651A (en) * | 2018-06-13 | 2018-10-02 | 宣城晶瑞新材料有限公司 | A kind of preparation of novel nano zirconia material |
| CN108640677A (en) * | 2018-06-22 | 2018-10-12 | 万华化学集团股份有限公司 | A kind of nano composite oxides zirconium powder preparation that crystallite dimension is controllable |
| CN112811903A (en) * | 2021-01-12 | 2021-05-18 | 浙江金琨锆业有限公司 | Remove Cl in zirconia powder-Method (2) |
| CN113200567A (en) * | 2021-05-26 | 2021-08-03 | 先导薄膜材料有限公司 | High-sintering-activity zirconium oxide powder and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 齐聪颖: "纳米氧化锆超重力共沉淀-水热法制备、分散及应用性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521142A (en) * | 2022-10-09 | 2022-12-27 | 中国科学院赣江创新研究院 | Rare earth doped hafnium oxide nano powder and preparation method and application thereof |
| CN116161958A (en) * | 2022-12-27 | 2023-05-26 | 中铝广西有色稀土开发有限公司 | Preparation method of yttrium-stabilized zirconia nano-powder |
| CN116354716A (en) * | 2023-04-06 | 2023-06-30 | 南京金鲤新材料有限公司 | Preparation process of zirconia powder with high sintering activity and low specific surface area |
| CN117228715A (en) * | 2023-11-10 | 2023-12-15 | 琥崧科技集团股份有限公司 | Preparation method of zirconium dioxide sintered body |
| CN117228715B (en) * | 2023-11-10 | 2024-01-30 | 琥崧科技集团股份有限公司 | Preparation method of zirconium dioxide sintered body |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114014651B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114014651B (en) | Method for producing nano composite zirconia powder by hydrothermal method | |
| CN101182197B (en) | W-Sn nano composite metal oxide gas-sensing material and preparation method thereof | |
| JP2011505332A (en) | Nanoparticle composition and method for producing the same | |
| CN104108749B (en) | A kind of preparation method of strontium titanate doping | |
| JPS6317221A (en) | Crystalline titanium oxide sol and production thereof | |
| CN106986381A (en) | A kind of loose preparation method containing zirconium hydroxide or nm-class powder of zirconium oxide | |
| JP3284413B2 (en) | Method for producing hydrated zirconia sol and zirconia powder | |
| CN102502798A (en) | Preparation method for monodisperse barium titanate nanopowder | |
| US7829061B2 (en) | Zirconium oxide hydrate particles and method for producing the same | |
| CN101117236B (en) | Method for preparing crystal system controlled indium oxide powder | |
| JP2004107186A (en) | Method for manufacturing nanosphere particle ceria compound powder having easy sintering property | |
| TW558470B (en) | Method for preparing high quality barium-titanate based powder | |
| CN110697776A (en) | Preparation method of spherical nano chromium sesquioxide | |
| CN109019676B (en) | Method for preparing high-purity nano-grade barium titanate by precipitation method | |
| JPS62187116A (en) | Production of pzt type piezoelectric ceramic powder sinterable at low temperature | |
| CN1458118A (en) | Process for preparing nano permanent magnetic ferrite powder | |
| KR100503858B1 (en) | Preparation of Nano-sized Crystalline Titanic Acid Strontium Powder from Aqueous Titanium Tetrachloride and Strontium Carbonate Solutions Prepared by Use of Inorganic Acids | |
| JPS63210027A (en) | Crystalline titanium oxide-tin oxide sol and production thereof | |
| CN102786302A (en) | Method for producing barium titanate from titaniferous solution as raw material | |
| CN104311074B (en) | A kind of submicron hercynite and its production and use | |
| CN1328211C (en) | Nanometer ferrite powder preparation method | |
| JPS61251516A (en) | Production of perovskite type oxide | |
| WO2024045201A1 (en) | Alumina ceramic powder with high sintering activity and preparation method therefor | |
| CN118164751A (en) | Barium calcium titanate powder, and preparation method and application thereof | |
| KR100503857B1 (en) | Preparation of Nano-sized Crystalline Titanic Acid Barium Powder from Aqueous Titanium Tetrachloride and Barium Chloride Solutions Prepared by Use of Inorganic Acids |
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 |