CN114014651B - Method for producing nano composite zirconia powder by hydrothermal method - Google Patents
Method for producing nano composite zirconia powder by hydrothermal method Download PDFInfo
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- CN114014651B CN114014651B CN202111066618.4A CN202111066618A CN114014651B CN 114014651 B CN114014651 B CN 114014651B CN 202111066618 A CN202111066618 A CN 202111066618A CN 114014651 B CN114014651 B CN 114014651B
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- powder
- zirconia
- yttrium
- zirconium
- hydrothermal
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000000843 powder Substances 0.000 title claims abstract description 129
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000227 grinding Methods 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 27
- 150000003839 salts Chemical class 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
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 62
- 239000002131 composite material Substances 0.000 claims description 44
- 239000012065 filter cake Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 33
- 230000001276 controlling effect Effects 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000005086 pumping Methods 0.000 claims description 21
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 16
- 238000012986 modification Methods 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 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 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 238000000889 atomisation Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 11
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 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
- 238000004537 pulping Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 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
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 238000004448 titration Methods 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
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 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
- 238000010345 tape casting Methods 0.000 abstract description 2
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 description 22
- 230000002776 aggregation Effects 0.000 description 15
- 238000005054 agglomeration Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- -1 grinding Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia 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
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction 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
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003292 glue Substances 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture 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
- 239000011164 primary particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011163 secondary particle Substances 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010067482 No adverse event 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
- 238000003917 TEM image Methods 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
- 229910007746 Zr—O Inorganic materials 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
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 235000019270 ammonium chloride Nutrition 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 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
- 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
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- KQHQLIAOAVMAOW-UHFFFAOYSA-N hafnium(4+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[Zr+4].[Hf+4] KQHQLIAOAVMAOW-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade 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
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane 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
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 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
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000012498 ultrapure water Substances 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
- VWQVUPCCIRVNHF-LZFNBGRKSA-N yttrium-95 Chemical compound [95Y] VWQVUPCCIRVNHF-LZFNBGRKSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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 application 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 carrying out specific hydrothermal precursor organic treatment. The application comprises the following steps: zirconium and yttrium soluble salt water dissolving, filtering, alkalizing, washing, hydrothermal, atomizing drying, calcining, grinding, surface modifying, granulating, packaging and the like. The application uses advanced low-cost and differential hydrothermal method to process, so that the product completely meets the manufacturing requirements in the dental field and replaces the like products of Tosoh corporation in Japan; the ratio of zirconium to yttrium and the calcining temperature are changed, the granulated powder is degummed at low temperature, and air flow is ground to obtain natural powder which is used for manufacturing an electronic ceramic-oxygen sensor and is smaller than 300 nanometers, and the method is most suitable for a tape casting molding process and is a domestic initial source.
Description
Technical Field
The application belongs to the field of new dental and electronic ceramic materials, and particularly relates to a method for producing nano composite zirconia powder by a hydrothermal method.
Background
In the background of global population aging, oral diseases become important factors affecting the life quality of people, and currently crafted porcelain teeth are easy to cause gum allergy and metal micro-leakage due to metal crown bottoms. The flexural strength of the zirconia denture is approximately three times higher than that of the porcelain tooth, the hardness is about twice that of the zirconia denture, the zirconia denture has strong chewing resistance, is insoluble in saliva and acid-base food, has no adverse reaction and cytotoxicity, is considered as a twin brother of the original tooth by the medical community, and has wide application prospect in the medical field; along with the development of society and technology, the sensor types are added with sensors with functions of various positions such as flow, positioning, gas concentration, speed, brightness, dryness and humidity, distance and the like from the earliest water temperature and pressure sensors. The oxygen sensor of the electronic fuel injection engine has the main functions of reducing environmental pollution caused by automobile exhaust emission and improving the fuel combustion quality of the automobile engine by signal transmission feedback and regulating and controlling the air-fuel ratio, and has great significance in advocating energy conservation and emission reduction to cope with climate change.
Because the zirconia false tooth has a high imitation appearance which is warm and moist like jade, excellent mechanical property and high biocompatibility, and an oxygen sensor with complex working conditions are all ceramic elements which can not be replaced in daily life of people, the application range is wide, the market capacity is large, the manufacturing precision is high, the quality of powder requiring 'ten thousand ceramic sources' is improved by a new step, and the zirconia powder and a partition membrane heat-resistant enhancement main inorganic additive of a ceramic product thereof are nano zirconia superfine powder by a hydrothermal method. The novel material is smooth in domestic raw materials, novel manufacturing equipment is mature, new and old markets are alternately developed, novel materials are produced by utilizing a novel process, and the novel energy lithium battery anode coating material and the solid electrolyte (LLZO for short) which are environment-friendly and have zero emission have wide development prospect.
At present, the production process of the domestic zirconia powder is mainly that zirconium oxychloride is doped with yttrium chloride, and the zirconium oxychloride is subjected to dissolution, filtration, ammonia precipitation, filter pressing washing, high-temperature calcination of filter cakes, grinding, gel adding granulation, sieving, mixing and packaging, and the process is commonly called as a coprecipitation process in the industry, and has the advantages of multiple lattice defects, high intra-crystal porosity and serious grain aggregation. Even in a preferential state, the obtained zirconia powder has small sintering density, large ceramic grains, low bending strength, low energy density and poor light transmittance when being used for ceramic manufacture.
Disclosure of Invention
The application provides a method for producing nano composite zirconia powder by a hydrothermal method, which can form an effective crystallization mechanism by changing a preparation process without specific organic treatment of a hydrothermal precursor, thereby completing the elusive microscopic process of nucleation-growth-crystallization, reducing the unit energy consumption of a finished product by 20 percent and improving the yield by 3 percent compared with the unit energy consumption of the finished product.
In order to achieve the above purpose, the application adopts the following technical scheme:
a method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
(1) Mixing zirconium and yttrium soluble salts, wherein the ratio of the zirconium to the yttrium soluble salts is converted into the mass ratio of oxides: 91.2% or 94.2% of zirconia and the balance of corresponding yttria, adding water to dissolve the mixture and water in a mass ratio of 1:1, stirring for half an hour, filtering, titrating with ammonia water simultaneously, controlling the pH value of the instant reaction to be 8.5-9.5, setting a fixed filter pressing-washing mode, and carrying out four rounds of washing to obtain an ammonia precipitation hydroxide filter cake; the chemical reaction involved in this section is as follows:
ZrOCl 2 +2NH 3 ﹒H 2 O——ZrO（OH） 2 ↓+2NH 4 Cl
YCl 3 +3NH 3 ﹒H 2 O——Y（OH） 3 ↓+3NH 4 Cl；
the wet method for producing composite zirconia has been quantitatively produced in China for less than twenty years, and belongs to novel materials which can not be replaced and are necessary for the market. Zirconium oxychloride (calculated by zirconia) is doped with 5.4 percent of yttrium oxide and 0.25 percent of aluminum oxide (yttrium and aluminum are mixed with zirconium oxide ions in the form of soluble salts), water is added for dissolution, filtration and the mixture is subjected to a co-titration reaction with ammonia water to generate amorphous hydrated hydroxide precipitate. The process selects undoped alumina, and the zirconium-yttrium ratio is different from the traditional coprecipitation process;
(2) Adding water into the filter cake obtained in the step (1) with the mass ratio of water being 1:1.5, simultaneously adding triethanolamine which is folded into zirconia with the mass ratio of 3-4%, adding the triethanolamine into a titanium reaction kettle, stirring at 1200rpm for 40 minutes to prepare slurry, adjusting the rotating speed to 80rpm, carrying out hydrothermal reaction at the heating rate of 2 ℃/min to 135-145 ℃, maintaining the kettle pressure at 0.25-0.45MPa for 16-32 hours, cooling, press-filtering, washing to obtain an yttrium-doped hydrous zirconia filter cake,
hydrothermally treated hydrous zirconia slurry, zirconium oxygen atoms are bonded with O-Zr-O bond raw materialThe nucleation of the position, the growth of growth is slow under the hydrothermal temperature, zirconium and oxygen atoms in the crystal lattice are arranged in a regular periodic variation way, the porosity in the crystal is low, the impurity content is low, the purity and the degree of self-formation of the crystal are high, and the chlorine ions which are not eluted are simply adsorbed on a filter cake and are easy to wash to ppm level, so that the adjacent particles are reduced due to Cl - Forming 'salt bridge' agglomeration, wherein a filter cake formed by the slurry is slightly dissolved in strong acid and aqua regia; in the prior art, a hydrothermal process is not established, the obtained hydrous zirconium yttrium hydroxide belongs to amorphous precipitation, is easily dissolved in strong acid and aqua regia, forms unordered aggregation state of atoms constituting a matrix, wraps impurities, and has a chloride ion washing equilibrium concentration as high as 300ppm;
(3) Adding water into the hydrated zirconia filter cake obtained in the step (2) in a mass ratio of 1:1.5, stirring at 1200rpm for 1 hour to prepare slurry, pumping the slurry into a drying tower, adjusting the inlet temperature of the drying tower to 220-240 ℃, adjusting the slurry flow rate, controlling the outlet temperature to 90-100 ℃, and obtaining natural fluffy drying powder;
the section adopts a mode of carrying out low-temperature flash evaporation dehydration by atomization drying, so that 'liquid bridge' agglomeration is reduced, the dried powder is in a natural loose state, the distance between adjacent particles is increased, and high-temperature calcination is facilitated, so that 'oxygen bridge' agglomeration is reduced.
In the prior art, the low-temperature rapid dehydration is carried out without setting an atomization drying mode, and when the high-temperature calcination is carried out, the residual adsorbed water in the filter cake is used for tensioning a plurality of adjacent particles due to surface tension, lattice deformities in crystals are overlapped, so that 'liquid bridge' and 'oxygen bridge' agglomeration are extremely easy to form, hard agglomeration is formed among the particles, and the later grinding dispersion and ceramic sintering are not facilitated;
(4) Calcining the dried powder obtained in the step (3) at a high temperature, and setting up a push plate speed for keeping the material in a high temperature area for 2-3 hours to obtain nano composite zirconia powder with high softness, crystallization degree, single dispersion degree, powder activity and thermal stability;
the intermediate of the existing calcination process is a filter cake with serious agglomeration degree, and because the filter cake contains a large amount of structural water and adsorbed water, high-concentration 'liquid bridge' agglomeration is easy to form under the action of water molecules; the dehydrated amorphous filter cake has more surface atoms, large energy and tight contact, and the lattice is irregularly 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) at a mass ratio of 1:1, grinding at a speed of 600rpm, grinding with zirconia grinding balls with a diameter of 0.3mm, controlling the median particle diameter of the slurry to be 220-250 nanometers to obtain composite zirconia slurry, adding modified polyacrylic acid D-305 and dry zirconia at a mass ratio of 100:0.8-1.2 and polyethylene glycol with a molecular weight of 400 and dry zirconia at a mass ratio of 100:1.5-2.5, carrying out surface modification, stirring at a rotating speed of 300rpm for 1 hour, setting the inlet temperature of a granulating tower to be 200-220 ℃, controlling the outlet temperature to be 90-105 ℃ by using a feeding flow rate, atomizing disc frequency to be 42HZ, carrying out spray granulation, sieving the granulating powder with a 100-mesh screen, taking out mixed packaging, and obtaining the finished granulating powder;
high dispersion is one of the important indicators of powder. The process is controlled by 'three bridges' which cause powder agglomeration, so that the calcined powder forming false agglomeration is easily scattered in a grinding pulping working section to form monodisperse ultrafine particles, and the slurry has high fluidity and uniform stability;
the existing process has the same calcining temperature and heat preservation time, the same solid content of 50 percent, grinding to 500 nanometers, thickening of slurry viscosity, extremely poor fluidity and even blockage of a pump pipe, so that the process cannot be advanced;
(6) Changing the doped yttrium oxide in the step (1) into 5 moles and the doped zirconium oxide into 95 moles, preserving the temperature of the granulated powder obtained in the step (5) for 2 hours at 380 ℃, cooling, performing air grinding, adjusting the vibration frequency of a feeder to 1500 times/min, and the air grinding pressure to 0.80MPa to obtain natural powder which is free from agglomeration and stable for a long time to be less than 300 nanometers;
the natural powder with the particle size smaller than 300 nanometers can be obtained by grinding simply, the natural powder is required to be paved by using hydrothermal treatment, the crystallization degree is high, the monodispersion degree is high, and then the superfine powder with the stable period more than 1 year can be obtained by effective surface modification; the common non-hydrothermal method powder, the proper hydrothermal temperature and the proper heat preservation time are not established, the proper surface modification and degumming temperature are not matched, even if the composite zirconia powder with the particle size smaller than 300 nanometers is obtained through sanding-air flow grinding, the composite zirconia powder cannot be in a natural loose state for a long time, and the composite zirconia powder is aggregated mutually and is in a low-energy stable state because of high energy generated by lattice defects, so that the particle size of the powder is secondarily grown.
In the steps, when the ratio of the zirconium to the yttrium soluble salts is converted into the mass ratio of oxides: 94.2% of zirconia and 5.8% of yttria, 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 is taken to obtain finished granulated powder;
when the ratio of the zirconium and yttrium soluble salts is converted into the mass ratio of oxide: 91.2% of zirconia and 8.8% of yttria, wherein the high-temperature calcination temperature in the step (4) is 1140-1150 ℃;
the zirconium soluble salt in the step (1) is zirconium oxychloride, zirconium nitrate, zirconium sulfate or zirconium tetrachloride, the yttrium soluble salt is yttrium chloride, yttrium nitrate and yttrium sulfate, and 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 the 8% ammonia water is preferably used as a zirconium yttrium precipitator; the dissolution stirring speed of the zirconium yttrium mixed salt is 1200rpm; the water in the process is deionized water; the fixed filter-pressing washing mode is as follows: and (3) filter cake: water mass ratio=1:4, stirring for 40 minutes at a stirring speed of 1200rpm, air pressure pressed into the plate-and-frame filter of 0.40MPa, and filter cloth model 750B; except for special description, all the proportions of the materials are mass ratios; the mass ratio of the mixed zirconium oxychloride and yttrium chloride solution to water is based on the mass data of zirconium oxychloride; all particle sizes are average particle sizes: the method comprises the steps of calcining powder in the step (4), granulating powder in the step (5), primary crystal grain size (also called lattice spacing and called primary grain size in the industry) of natural powder in the step (6) of less than 300 nanometers, grinding grain size (called secondary grain size in the industry) of composite zirconia slurry in the step (5), granulating powder grain size and natural powder grain size (called tertiary grain size in the industry) of less than 300 nanometers; 5 mol of yttrium oxide and 95 mol of zirconium oxide are converted into 8.8 percent of yttrium oxide and 91.2 percent of zirconium oxide by mass ratio; the zirconia according to the present application is essentially a hafnium zirconium oxide content of about 1.8% hafnium oxide, as is zirconium oxychloride, with a 5Y (short for 5 molar yttrium oxide) zirconium oxide content of91.2%, containing hafnium oxide, all the zirconium oxides referred to hereinbefore and hereinafter; the dental powder proportion of 5.8 percent of yttrium oxide and 94.2 percent of zirconium oxide is conventionally classified into 3 mol of yttrium oxide, namely 3Y-ZrO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the 5Y composite zirconia used for the electronic ceramic particle size is smaller than 300 nanometers natural powder, the particle size cannot be changed in a large range through the gas pressure and the gas grinding times of an air flow mill, the main process is used for laying, the air flow mill simply breaks up soft agglomerates formed by degumming the granulated powder at a low temperature to restore the original parameters, the particle size range is generally between 260 and 290 nanometers, the data is not balanced and controlled by the air flow mill section, is a necessary value, is extremely small in relation to the regulation of the gas pressure and the gas grinding times and can be ignored, and specific parameters smaller than 300 nanometers are not expressed in the embodiment as control values;
the "organized treatment" in the "… specific hydrothermal precursor organized treatment" of the description abstract refers to 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, and before hydrothermal reaction, a conversion form of the organic zirconium is generated in the process, so that the manufacturing cost and the difficulty in recycling the organic salt are increased, which is one of the low cost reasons of the application, because the organic zirconium is converted from zirconium oxychloride, which is the basic raw material with the highest cost performance of zirconium salt;
the abstract of the specification, step (6) in claim 1 and step (6) of the specification (the former and later are the same) refer to that 'granulated powder is degummed at 380 ℃ at low temperature', wherein 'glue' refers to the sum of all organic matters added in grinding pulping, and industry habit is called 'glue', and supplementary explanation is given here.
The beneficial effects are that: the application provides a method for producing nano composite zirconia powder by a hydrothermal method, which adopts an advanced hydrothermal method production process, focuses on the integrity of powder nucleation-growth-development, the consistency of crystal grains and the reduction of three-bridge aggregation such as salt bridge-liquid bridge-oxygen bridge and the like, forms a novel dental and electrical functional ceramic material with high crystallization degree, less impurities in the crystal, low pores, high monodispersity, good sintering activity, high product hardness, high bending strength and high light transmittance, and the material characteristics are that under the premise of certain chemical purity, crystal lattices supporting the powder develop and grow in a good environment, and belongs to high-purity self-shaped crystals; the powder particles have high monodispersion degree, are uniformly mixed, and are in atomic distance contact with each other; the technological parameters are set reasonably, the primary grain size (primary grain size) is in a quasi-nanometer state, the macroscopic size of the 5Y electronic ceramic powder is below 300 nanometers, and the technology is the first initiation in China, which is most suitable for small thin or special-shaped electronic ceramics such as oxygen sensors formed by a tape casting method.
The composite zirconia powder produced by the effective hydrothermal method is applied to the fields of dental materials, biomedical treatment including oxygen sensors, lithium battery anode coating, solid electrolyte, intelligent wearing, electronic communication, sky sea and the like, and the performance of downstream products is greatly improved.
Drawings
FIGS. 1 and 2 are TEM views of composite zirconia powder obtained in the embodiment of the present application;
FIGS. 3 and 4 are XRD patterns of composite zirconia powder obtained in the examples of the present application;
FIGS. 5 and 6 are graphs showing particle size distribution diagrams of milled composite zirconia slurry obtained in examples of the present application;
FIG. 7 is a graph showing the distribution of the particle size of natural powder of less than 300 nm obtained by low-temperature degumming and air grinding of 5Y granulated powder in the embodiment of the application
Fig. 8 is a desorption graph of the composite zirconia powder obtained in the example of the present application.
Detailed Description
The application is described in detail below with reference to the attached drawings and the specific embodiments:
example 1
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 54.5Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the reaction pH value to 8.5 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and press-filtering for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into 3% of zirconia by mass ratio, stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 135 ℃ at the speed of 2 ℃/min, maintaining the kettle pressure to be 0.25MPa for hydrothermal, cooling, performing multiple times of press-filtering and washing until the chloride ions of the filtrate is less than 5ppm, adding water into the filter cake 1:1.5 after hydrothermal stirring for 1:1 rpm for 1 hour according to the washing mode, pumping into a drying tower, designing an inlet temperature of 220 ℃, controlling an outlet temperature of 90 ℃ by using a feeding flow rate, carrying out atomization drying, putting the hydrothermal dried powder into a sagger, staying for 3 hours at a high temperature area of 1030 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, putting into a nano sand mill for grinding at 600rpm, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling a median particle size to 220 nm, obtaining composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 distributed by Zhongjing grease Co., japan, carrying out surface modification with a mass ratio of 100:0.8 and polyethylene glycol with an added molecular weight of 100:2.5, carrying out surface modification with a rotating speed of 120rpm, setting an inlet temperature of 200 ℃ of the granulating tower, controlling an outlet temperature of 90 ℃ by using a feeding flow rate, carrying out atomization disc frequency of 42HZ, carrying out spray granulation, sieving the granulated powder with a 100-mesh screen, mixing the undersize products, and packaging to obtain the finished product granulation powder.
Example 2
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 54.5Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the reaction pH value to 9.5 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and press-filtering for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into zirconia with the proportion of 4% for stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 145 ℃ at the speed of 2 ℃/min, maintaining the kettle pressure to be 0.45MPa for hydrothermal, cooling, performing multiple times of press-filtering and washing until the chloride ions of the filtrate is less than 5ppm, stirring the filter cake 1:1.5 after hydrothermal stirring for 1:1 rpm for 1 hour according to the washing mode, pumping into a drying tower, designing an inlet temperature of 240 ℃, controlling an outlet temperature of 100 ℃ by using a feeding flow rate, carrying out atomization drying, placing the hydrothermal dried powder into a sagger, staying for 2 hours at a high temperature zone of 1040 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, putting into a nano sand mill for grinding at 600rpm, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling the median particle size to 250 nanometers, obtaining composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 distributed by Zhongjing grease Co., japan, carrying out surface modification with a mass ratio of 100:1.2 and polyethylene glycol with an added molecular weight of 400 in a mass ratio of 100:1.5, carrying out surface modification with a rotating speed of 120rpm, setting an inlet temperature of 220 ℃ of the granulating tower, controlling an outlet temperature of 105 ℃ by using a feeding flow rate, carrying out spray granulation with an atomizing disc frequency of 42HZ, sieving the granulated powder with a 100-mesh screen, mixing the undersize products, and packaging to obtain the finished product granulation powder.
Example 3
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 54.5Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the pH value of the reaction to be 9.0 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and pressing for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into zirconia with the proportion of 3.5%, stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 137 ℃ at the speed of 2 ℃/min, pressing for 0.37MPa for hydrothermal, maintaining for 27 hours, cooling, washing by multiple times of pressing and washing until the chloride ions of the filtrate is less than 5ppm according to the washing mode, adding water into the filter cake 1:1.5, stirring at the rotating speed of 1200rpm for 1 hour, pumping into a drying tower, designing an inlet temperature of 230 ℃ and controlling an outlet temperature of 95 ℃ by using a feeding flow rate, carrying out atomization drying, putting the hydrothermal dried powder into a sagger, staying for 2.5 hours at a high temperature area of 1035 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, putting into a nano sand mill for grinding at 600rpm, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling the median particle size to 230 nanometers, obtaining composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 distributed by Zhongjing grease Co., japan, carrying out surface modification with a mass ratio of 100:1.0 and a polyethylene glycol with an added molecular weight of 400, carrying out surface modification with a mass ratio of 100:2.0, setting the inlet temperature of the granulating tower at 210 ℃ after stirring for 1 hour, controlling the outlet temperature of 95 ℃ by using the feeding flow rate, carrying out spray granulation with an atomizing disc frequency of 42HZ, and sieving the granulated powder with a 100 mesh screen, mixing the undersize products, and packaging to obtain the finished product granulation powder.
Example 4
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 85.4.5Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the reaction pH value to 8.5 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and pressing for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into 3% of zirconia in mass ratio, stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 135 ℃ at the speed of 2 ℃/min, pressing for 0.25MPa for hydrothermal, maintaining for 32 hours, cooling, filtering and washing until the chloride ions of the filtrate is less than 5ppm through multiple times, adding water into the filter cake 1:1.5, stirring at the speed of 1200rpm for 1 hour, pumping into a drying tower, designing an inlet temperature of 220 ℃, controlling an outlet temperature of 90 ℃ by using a feeding flow rate, carrying out atomization drying, placing the hydrothermal dried powder into a sagger, staying for 3 hours at a high temperature area of 1140 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, putting into a nano sand mill for grinding at 600rpm, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling a median particle size to 220 nm to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid type D-305 distributed by Zhongjing grease Co., japan, carrying out surface modification with a mass ratio of 100:0.8 and polyethylene glycol with an added molecular weight of 100:2.5, carrying out surface modification with a rotating speed of 120rpm, setting an inlet temperature of 200 ℃ of the granulating tower, controlling an outlet temperature of 90 ℃ by using a feeding flow rate, carrying out atomization disc frequency of 42HZ, carrying out spray granulation, drying and heat preservation for 2 hours at 380 ℃ and cooling the granulated powder, performing air grinding, and adjusting the vibration frequency of the feeder to 1500 times/min, wherein the air grinding pressure is 0.80MPa, so as to obtain another finished product of the composite zirconia natural powder with the diameter smaller than 300 nanometers.
Example 5
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 85.4Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the reaction pH value to 9.5 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and press-filtering for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into zirconia with the proportion of 4% for stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 145 ℃ at the speed of 2 ℃/min, maintaining the kettle pressure to be 0.45MPa for hydrothermal, cooling, performing multiple times of press-filtering and washing until the chloride ions of the filtrate is less than 5ppm, stirring the filter cake 1:1.5 after hydrothermal stirring for 1:1 rpm for 1 hour according to the washing mode, pumping into a drying tower, designing an inlet temperature of 240 ℃, controlling an outlet temperature of 100 ℃ by using a feeding flow rate, carrying out atomization drying, placing the hydrothermal dried powder into a sagger, staying for 2 hours at a high temperature area of 1150 ℃ to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, putting into a nano sand mill for grinding at 600rpm, grinding with a zirconia grinding ball with a diameter of 0.3mm, controlling a median particle size to 250 nanometers to obtain composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid type D-305 distributed by the oil and fat company of Japan, carrying out surface modification with a mass ratio of 100:1.2 and polyethylene glycol with an added molecular weight of 400 in a mass ratio of 100:1.5, carrying out surface modification with a rotating speed of 120rpm, setting an inlet temperature of 220 ℃ of the granulating tower, controlling an outlet temperature of 105 ℃ by using a feeding flow rate, carrying out spray granulation with an atomizing disc frequency of 42HZ, drying and preserving heat for 2 hours at 380 ℃, cooling the granulated powder, performing air grinding, and adjusting the vibration frequency of the feeder to 1500 times/min, wherein the air grinding pressure is 0.80MPa, so as to obtain another finished product of the composite zirconia natural powder with the diameter smaller than 300 nanometers.
Example 6
A method for producing nano composite zirconia powder by a hydrothermal method, which comprises the following steps:
weighing 360Kg of high-purity zirconium oxychloride (36% of zirconia), 85.4Kg of yttrium chloride solution (14.65% of yttria), putting into a dissolution kettle containing 360Kg of pure water, stirring for 30 minutes, filtering, dripping into another reaction kettle together with 8% of ammonia water, controlling the pH value of the reaction to be 9.0 in a stirring state, aging and stirring for 40 minutes after the reaction is finished, pressing 0.40MPa air into a plate frame for filtering, adding water into a filter cake 1:4, stirring for 40 minutes, pressing 0.40MPa air into the plate frame for filtering, washing and pressing for four times, adding water into the filter cake 1:1.5, adding triethanolamine which is folded into zirconia with the proportion of 3.5%, stirring for 1 hour, pumping into a titanium reaction kettle, increasing the speed to 137 ℃ at the speed of 2 ℃/min, pressing for 0.37MPa for hydrothermal, maintaining for 27 hours, cooling, washing by multiple times of pressing and washing until the chloride ions of the filtrate is less than 5ppm according to the washing mode, adding water into the filter cake 1:1.5, stirring at the rotating speed of 1200rpm for 1 hour, pumping into a drying tower, designing an inlet temperature of 230 ℃ and controlling an outlet temperature of 95 ℃ by using a feeding flow rate, carrying out atomization drying, putting the hydrothermal dried powder into a sagger, staying at a high temperature area of 1145 ℃ for 2.5 hours to obtain composite zirconia calcined powder, adding water into the composite zirconia calcined powder in a ratio of 1:1, grinding the composite zirconia calcined powder into a nano sand mill at 600rpm, grinding the composite zirconia calcined powder with a zirconia grinding ball with a diameter of 0.3mm, controlling the median particle size to 230 nanometers, obtaining composite zirconia slurry, pumping into a storage tank, adding modified polyacrylic acid D-305 distributed by Zhongjing grease Co., ltd, carrying out surface modification by adding polyethylene glycol with a molecular weight of 400 in a mass ratio of 100:1.0, setting the inlet temperature of the granulating tower at 210 ℃ by using the feeding flow rate, controlling the outlet temperature of 95 ℃ and the frequency of an atomizing disc at 42HZ, carrying out spray granulation, drying and preserving the granulating powder at 380 ℃ for 2 hours, performing air grinding, and adjusting the vibration frequency of the feeder to 1500 times/min, wherein the air grinding pressure is 0.80MPa, so as to obtain another finished product of the composite zirconia natural powder with the diameter smaller than 300 nanometers.
The washing water related to the step 1) and the step 2) can be reused, namely the washing water of the last time after the hydrothermal process is used for washing the filter cake of the fourth time before the hydrothermal process, the return water of the last time after the hydrothermal process is used for washing the filter cake of the third time before the hydrothermal process, the return water of the third time before the hydrothermal process is used as the washing water of the filter cake of the first time, and the return water of the fourth time before the hydrothermal process is used as the washing water of the filter cake of the second time. And then evaporating the high-concentration washing water by a triple-effect evaporator, recovering ammonium chloride, and recycling condensate as high-purity water into a production line. This step is not included in the main process of the present application and is outlined herein.
The characterization test was performed on the resulting product, with the following results:
FIGS. 1 and 2 are TEM images of composite zirconia obtained in example 3 and example 6, respectively, from which it can be seen that the average sizes of the powder primary crystals are 50nm and 40 nm, respectively;
FIGS. 3 and 4 are X-ray diffraction patterns of the composite zirconia powder obtained in examples 1 to 3 and examples 4 to 6, respectively, and it can be seen from the figures that the powder in FIG. 3 has a tetragonal phase of 94% and a monoclinic phase of 6%; FIG. 4 shows a 100% tetragonal phase;
fig. 5 and 6 are particle size distribution diagrams of the calcined powder prepared and ground in example 3 and example 6, respectively, wherein the average particle sizes are 230 nm and 240 nm, respectively, and the particle size distribution of the slurry is very narrow as can be seen from the diagrams;
FIG. 7 is a graph showing the particle size distribution of the natural powder of example 6 less than 300 nm after 13 months of storage, wherein the average particle size is 270 nm, no agglomeration is caused, and the powder particle size distribution is very narrow as can be seen intuitively from the graph;
FIGS. 8-1 and 8-2 are graphs showing desorption of the composite zirconia powder obtained in example 3 and example 6, respectively, according to the present application, from which it can be seen that 8-1 is the composite zirconia powder obtained in example 3The specific surface area of the product granulation powder is 10.33m 2 The peak 8-2 of the powder is that the specific surface area of the natural powder of the example 6 is less than 300 nanometers and is 10.44m 2 /g。
Table 1 characterization comparison of the inventive product with similar products provided by customers
| Index producing area | ZrO 2 | Y 2 O 3 | Primary particle diameter | Secondary particle size | Three times particle diameter | Specific surface area |
| The application is that | 94.2% | 5.8% | 50nm | 230nm | 52um | 10.33m 2 /g |
| Japanese Tongcao | 94.5% | 5.25% | 36nm | 90nm | 55um | 13.2m 2 /g |
The powder of Japanese Dong Cao Chike is doped with 0.25% Al 2 O 3 。
TABLE 2 comparison of test data of the sintered denture of the product of the application and the like with national standards
| Index producing area | Light transmittance | Rockwell hardness | Sintered density | Flexural Strength | Fracture toughness |
| The application is that | 43% | HRC92 | 6.08g/cm 3 | 1100MPa | 6.5MPa﹒m 0.5 |
| Japanese Tongcao | 41% | HRC91 | 6.08g/cm 3 | 1100MPa | 6.6MPa﹒m 0.5 |
| National standard | 800MPa | 5.0MPa﹒m 0.5 |
In the national standard GB 30367-2013/ISO 6872:2008, no specific requirements are imposed on light transmittance (light transmittance), rockwell hardness and sintering density.
TABLE 3 characterization comparison of the products of the application with similar products offered by customers
| Index producing area | ZrO 2 | Y 2 O 3 | Primary particle diameter | Secondary particle size | Three times particle diameter | Specific surface area |
| The application is that | 91.2% | 8.8% | 40nm | 230nm | 270nm | 10.44m 2 /g |
| Japanese DKKK | 91.2% | 8.8% | 40nm | 250nm | 290nm | 11.0m 2 /g |
Table 4 shows comparison of test data of the sensor sintered by customers for the products of the application and the like
Tables 1 and 3 are 3Y-ZrO 2 Dental powder and 5Y-ZrO 2 The sensor powder is characterized in that tables 2 and 4 are respectively the comparison of parameters after sintering into porcelain by clients, and as can be seen visually from tables 2 and 4, the product of the application has similar performance with Japanese like products, and the 5Y electrical performance is higher than Japanese like products.
To facilitate an understanding of the electrical performance test parameters of table 4, test conditions and data are provided as follows:
sensor burn test electrical performance output characteristics
1) Detection conditions:
gas: combustion gas
Exhaust temperature: 350-400 DEG C
Exhaust environment: rich (λ=0.972±0.004) lean (λ=1.024±0.004)
Measurement item
And (3) outputting a rich combustion voltage: output Voltage (VR) in rich gas
Lean burn voltage output: output voltage in lean gas (VL)
Response time: (rich to lean): output 600= >300mV desired Time (TRL)
Response time: (lean to rich): time required to output 300= >600mV (TLR)
Sensor nernst cell internal resistance: rin (Rin)
Conclusion:
1. the signal jump amplitude (VR-VL) is 860-36mV, DKKK is 920-69mV, and the same ratio value is 60 and 33 respectively;
2. TRL value, the application is 70ms, DKKK is 93ms, the application is shorter and more stable;
3. TLR value, the application is 89ms, DKKK is 100ms, the application is time and more stable;
4. the product of the application has lower internal resistance and better activity of the sensing element.
Besides the application, the powder contains manganese oxide, ferric oxide, nickel oxide, cobalt oxide, magnesium oxide, titanium oxide, chromium oxide, aluminum oxide, barium titanate and binary or multi-component composite thereof, and the crystallinity, the dispersivity, the uniformity, the sinterability and the stability of the powder are improved, so that the energy density, the safety, the periodicity, the weather resistance, the long-acting property and the mechanical property of domestic electronic components and other functional ceramics are all of a qualitative leap, which is a recognized fact in the industry. Many electronic component manufacturing enterprises such as thermosensitive, photosensitive, sound-sensitive, pressure-sensitive, humidity-sensitive, magnetic-sensitive, capacitors, filters and the like still use a physical and mechanical mixing method at present, and then powder with the size of 0.5 microns is obtained by grinding, so that high-quality powder is obtained without considering crystal nucleation, lattice development and anti-agglomeration treatment.
It should be noted that when the yttrium oxide content reaches 4.0 mol, the light transmittance of the powder after porcelain formation can be improved to more than 46% by the process of the application; when the yttrium oxide content is increased to 5.0 mol, or other auxiliary agents are doped, main processes such as hydrothermal conditions, surface modification formula and the like are not changed, and the 300 nanometer composite zirconium oxide natural powder can be diversified, which is common in the industry and can be obtained without creative labor.
The above-listed examples merely aid in understanding the application and should not be construed as limiting the up-and-down adjustment of parameters within the critical limits of the process of the application in order to facilitate an understanding of the application. The scope of the application is not limited to the specific combination of the above technical features, but also covers other technical features formed by any combination of the above technical features or equivalent features without departing from the inventive concept. The technical solution formed by mutually replacing the above features and the technical features with similar functions disclosed in the application (but not limited to), without carrying out creative work, for a person skilled in the art, other related drawings and corresponding process flows can be obtained according to the drawings, and the same or similar performance as the product of the application can be obtained under the production process, which is included in the protection scope of the application, and the supplementary explanation is provided herein.
Claims (8)
1. The method for producing the nano composite zirconia powder by the hydrothermal method is characterized by comprising the following steps of:
(1) Mixing zirconium and yttrium soluble salts, wherein the ratio of the zirconium to the yttrium soluble salts is converted into the mass ratio of oxides: 91.2% or 94.2% of zirconia and the balance of corresponding yttrium oxide, adding water to dissolve zirconium yttrium mixed salt and water in a mass ratio of 1:1, filtering, titrating simultaneously with alkaline water, adjusting the pH value of the zirconium yttrium solution and the alkaline water flow control instant reaction to be 8.5-9.5, setting a fixed filter pressing-washing mode, and carrying out four rounds of washing to obtain an alkali precipitation hydroxide filter cake;
(2) Adding water into the filter cake obtained in the step (1) in a mass ratio of 1:1.5, adding triethanolamine which is folded into zirconia with a mass ratio of 3-4%, stirring for 40 minutes to prepare slurry, heating to 135-145 ℃ at a speed of 2 ℃/min, carrying out hydrothermal reaction, maintaining the pressure at 0.25-0.45MPa for 16-32 hours, cooling, press-filtering 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) in a mass ratio of 1:1.5, stirring for 1 hour to prepare slurry, and drying in a low-temperature dehydration mode by adopting atomization drying to obtain natural fluffy drying powder, wherein the atomization drying specifically comprises the following 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 outlet temperature of the slurry is controlled to be 90-100 ℃ by adjusting the slurry flow rate, the slurry stirring speed in the storage tank is 120 revolutions per minute, and the rotation frequency of an atomizing disk is 45Hz;
(4) Calcining the dried powder obtained in the step (3) at a high temperature, and staying in a high temperature area for 2-3 hours to obtain nano composite zirconia calcined powder; wherein when the ratio of the zirconium and yttrium soluble salts is converted into the mass ratio of oxide: 94.2% of zirconia and 5.8% of yttria, and the high-temperature calcination temperature is 1030-1040 ℃; when the ratio of the zirconium and yttrium soluble salts is converted into the mass ratio of oxide: 91.2% of zirconia and 8.8% of yttria, wherein the high-temperature calcination temperature is 1140-1150 ℃;
(5) Adding water into the calcined powder of the composite zirconia obtained in the step (4) in a mass ratio of 1:1, grinding to control the median particle diameter of the slurry to be 220-250 nanometers, obtaining composite zirconia slurry, pumping the slurry into a storage tank with stirring, adding modified polyacrylic acid type D-305 and polyethylene glycol with molecular weight 400 for surface modification, stirring for 1 hour, and then carrying out spray granulation to obtain granulated powder;
(6) And (3) carrying out air flow grinding on the granulated powder obtained in the step (5) after the temperature is kept at 380 ℃ for 2 hours, wherein the vibration frequency of a feeding machine is regulated to 1500 times/min, and the air grinding pressure is regulated to 0.80MPa, so as to obtain loose powder with the particle size less than 300 nanometers.
2. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1, wherein: the zirconium soluble salt in the step (1) 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; the mixing, water adding, dissolving and stirring speed of the zirconium and yttrium soluble salt is 1200 revolutions per minute, and stirring is carried out for 40 minutes; the type of the filter cloth is 750B; after titration with alkali, the stirring speed was 600rpm and the stirring was continued for 40 minutes.
3. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1 or 2, wherein: the zirconium soluble salt in the step (1) is zirconium oxychloride, the yttrium soluble salt is yttrium chloride, and the alkali is 8% ammonia water.
4. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1, wherein: and (3) adding water into the filter cake in the step (2), pulping and stirring, and washing and stirring the filter cake after hydrothermal treatment, wherein the stirring speed is 1200rpm, and the stirring speed is 80rpm after the slurry is transferred into a hydrothermal kettle.
5. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1, wherein: and (3) adding water into the filter cake to prepare slurry, wherein the stirring speed is 1200 revolutions per minute.
6. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1, wherein: the mass ratio of the modified polyacrylic acid type D-305 to the zirconia in the step (5) 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.
7. The method for producing nano composite zirconia powder by a hydrothermal method according to claim 1, wherein: the spray granulation in step (5) comprises the following steps: setting the inlet temperature of a granulating tower to be 200-220 ℃, controlling the stirring speed of slurry in a storage tank to be 120rpm, controlling the outlet temperature to be 90-105 ℃ by using the feeding flow rate, and performing spray granulation by using the rotating frequency of an atomizing disk to be 42 Hz.
8. The method for producing nano-composite zirconia powder by a hydrothermal method according to claim 7, wherein: and (5) sieving the granulated powder obtained in the step (5) with a 100-mesh screen, and taking the undersize to obtain the finished product of the granulated powder.
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