CN113248278A - Modified zirconia ceramic with surface compounded with bioactive substances and preparation method thereof - Google Patents
Modified zirconia ceramic with surface compounded with bioactive substances and preparation method thereof Download PDFInfo
- Publication number
- CN113248278A CN113248278A CN202110502544.8A CN202110502544A CN113248278A CN 113248278 A CN113248278 A CN 113248278A CN 202110502544 A CN202110502544 A CN 202110502544A CN 113248278 A CN113248278 A CN 113248278A
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- China
- Prior art keywords
- zirconia ceramic
- calcium
- silicon
- zirconia
- surface layer
- Prior art date
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 367
- 239000000919 ceramic Substances 0.000 title claims abstract description 155
- 230000000975 bioactive effect Effects 0.000 title claims abstract description 106
- 239000000126 substance Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002344 surface layer Substances 0.000 claims abstract description 79
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 35
- BXYHXVIURNMBJM-UHFFFAOYSA-N [P].[Si].[Ca] Chemical compound [P].[Si].[Ca] BXYHXVIURNMBJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000009715 pressure infiltration Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 17
- 239000004005 microsphere Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000003017 phosphorus Chemical class 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 229960005336 magnesium citrate Drugs 0.000 claims description 3
- 239000004337 magnesium citrate Substances 0.000 claims description 3
- 235000002538 magnesium citrate Nutrition 0.000 claims description 3
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 2
- 239000001354 calcium citrate Substances 0.000 claims description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims 1
- LAZOHFXCELVBBV-UHFFFAOYSA-N [Mg].[Ca].[Si] Chemical compound [Mg].[Ca].[Si] LAZOHFXCELVBBV-UHFFFAOYSA-N 0.000 abstract description 34
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000010410 layer Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000012466 permeate Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 4
- 239000012890 simulated body fluid Substances 0.000 description 15
- 239000011351 dental ceramic Substances 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 238000000576 coating method Methods 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- 210000001185 bone marrow Anatomy 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 9
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 8
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000014509 gene expression Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 5
- 239000001963 growth medium Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 5
- 229910052586 apatite Inorganic materials 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007943 implant Substances 0.000 description 4
- 210000000963 osteoblast Anatomy 0.000 description 4
- 230000009818 osteogenic differentiation Effects 0.000 description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000010478 bone regeneration Effects 0.000 description 3
- 238000003501 co-culture Methods 0.000 description 3
- -1 ion modified zirconia Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
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- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical group [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- 238000010304 firing Methods 0.000 description 2
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- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010018275 Gingival atrophy Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 208000008312 Tooth Loss Diseases 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000005313 bioactive glass Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 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 1
- 230000007547 defect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 201000005562 gingival recession Diseases 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 201000001245 periodontitis Diseases 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910001720 Åkermanite Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
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- A—HUMAN NECESSITIES
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- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/74—Fillers comprising phosphorus-containing compounds
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
-
- 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
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Abstract
The invention discloses a modified zirconia ceramic with a surface compounded with a bioactive substance and a preparation method thereof. The method comprises the following steps: preparing calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol; preparing a zirconium oxide suspension; preparing a zirconia ceramic having a porous surface layer; putting the zirconia ceramic with the porous surface layer into calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol by a negative pressure infiltration process, so that the bioactive sol is infiltrated into the porous surface layer, and carrying out heat treatment after drying to obtain the ceramic. According to the invention, calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances are loaded in the pore channels of the porous surface layer of the zirconia to endow the zirconia ceramic with high bioactivity, and the porous surface layer is combined with the zirconia ceramic and synchronously sintered, so that the problem of poor interface bonding strength of a surface active layer and a zirconia matrix material is solved; the bioactive substances only permeate into the porous surface layer, the internal matrix still keeps high density after sintering, and the mechanical property of the material is not obviously influenced.
Description
Technical Field
The invention relates to the field of medical materials for dental restoration, in particular to a modified zirconia ceramic with a surface compounded with bioactive substances and a preparation method thereof.
Background
Titanium and titanium alloy implants in metal implants have found widespread use in the clinical treatment of tooth loss due to dental caries, periodontitis, dental trauma and the like. However, there are problems such as blackening of titanium metal due to gingival atrophy and hypersensitivity due to release of toxic ions. The zirconia ceramic has good biocompatibility and chemical stability, excellent mechanical property and unique aesthetic effect, thereby becoming a dental prosthetic material with good clinical application prospect. The zirconia ceramics as inert materials have no bioactivity, and after being implanted into a body, the surrounding fibrous tissues can block the integration of the implant and the surrounding bone tissues, thereby causing implantation failure, so that the development of the bioactive zirconia dental repair materials has important significance.
In recent years, modified zirconia is generally subjected to surface modification by a coating method, but the coating method generally has the problem of mismatch of thermal expansion coefficients, so that residual stress exists, the bonding degree of a substrate and a coating interface is weak, the substrate and the coating interface can be dissolved and fall off in an oral cavity for a long time and are not suitable for clinical application, the mechanical strength of zirconia ceramics is seriously influenced due to phase change caused by the current surface modification means, the addition amount of bioactive substances and the types of the bioactive substances are limited, and the improvement on the biological performance is limited. CN112028626A discloses a method for preparing zirconia bioactive ceramics, which shows poor bonding degree due to residual stress caused by mismatch of thermal expansion coefficients of the coating and the substrate, and may cause coating peeling in long-term application. CN106904962B discloses a method for preparing bioactive zirconia dental ceramic material, in which the active substance existing in the grain boundary influences the mechanical property of zirconia, and the addition amount of the active substance is limited. CN109867520A discloses a zirconium oxide-based strontium, silicon and fluorine trace doped hydroxyapatite zirconium oxide toughened composite coating, a preparation method and application thereof, and the problem of coating falling caused by insufficient bonding degree exists. CN110917394A discloses the application of ion modified zirconia surface in the preparation of zirconia abutment or implant, and also has the problem of coating peeling caused by insufficient binding degree. The silver ion modified zirconia has improved antibacterial performance, but does not promote the proliferation and differentiation of cells.
The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has a stimulating effect on the gene expression of osteoblasts, and can obviously promote bone regeneration in clinical application. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has good bioactivity, biocompatibility, biodegradability and mechanical properties, releases active ions such as calcium, magnesium, silicon, phosphorus and the like, can induce the formation of a apatite layer, and is beneficial to the combination of materials and bone tissues. The deposition of wollastonite on the surface of porous alumina ceramic can obviously improve the bioactivity of the porous alumina ceramic and mineralize apatite. Diopside scaffolds induce apatite production, supporting human osteoblast adhesion, growth and alkaline phosphatase (ALP) expression. Therefore, the research of the zirconia dental ceramic which has high bioactivity and high strength and has high bonding strength between the surface modification layer and the matrix has important significance.
Disclosure of Invention
In order to overcome the defects that the conventional biological modified zirconia dental ceramic in the prior art cannot simultaneously have excellent biological activity and high mechanical strength, the invention aims to provide a modified zirconia ceramic with a surface compounded with a biological active substance and a preparation method thereof. The zirconia ceramic material has good biological activity, high mechanical property and simple preparation process.
The purpose of the invention is realized by at least one of the following technical solutions.
According to the preparation method provided by the invention, calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol is loaded in the pore channel of the porous surface layer of the zirconia, and the generated calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance is embedded in the pore channel of the surface layer of the zirconia through high-temperature heat treatment, so that the zirconia ceramic is endowed with high bioactivity. The porous surface layer is combined with zirconia ceramics and synchronously sintered, thereby solving the problem of poor interface bonding strength of the surface active layer and the zirconia matrix material; the bioactive substances only permeate into the porous surface layer, the internal matrix still keeps high density after sintering, the mechanical property of the material is not obviously influenced, and the problem that the conventional biological modified zirconia dental ceramic cannot have good bioactivity and high mechanical strength at the same time can be solved.
The preparation method of the modified zirconia ceramic with the surface compounded with the bioactive substances, provided by the invention, comprises the following steps:
(1) preparing calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol: adding a hydrolyzable silicon-containing compound, a water-soluble calcium salt, a water-soluble magnesium salt or a water-soluble phosphorus salt into deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, and carrying out hydrolytic polycondensation reaction to obtain calcium-magnesium silica sol or calcium-silicon-phosphorus sol;
(2) pressing and molding zirconia powder to prepare a zirconia ceramic green body, and heating for pre-sintering treatment to obtain a zirconia ceramic pre-sintered body;
(3) preparation of zirconia suspension: adding a pore-forming agent, a stabilizing agent, a dispersing agent and zirconia powder into a solvent, and uniformly mixing to obtain a suspension; dipping (dip-coating process) or spraying the suspension (high-stability and high-dispersity zirconia suspension) on the surface of the zirconia ceramic pre-sintered body (the suspension is permeated and adsorbed on the surface of the pre-sintered body) in the step (2), drying to form a pore-forming surface layer, and heating to perform sintering treatment to obtain the zirconia ceramic with the porous surface layer;
(4) soaking the zirconia ceramic with the porous surface layer in the step (3) in the calcium-magnesium-silica sol or calcium-silicon-phosphorus sol prepared in the step (1) in a container, performing negative pressure infiltration treatment (the calcium-magnesium-silica or calcium-silicon-phosphorus bioactive sol is infiltrated into the porous surface layer of the zirconia ceramic through the negative pressure infiltration treatment), taking out, standing, aging and drying to obtain the zirconia ceramic with the composite surface layer; and heating the zirconia ceramic with the compounded surface layer for heat treatment to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the compounded surface bioactive substances.
Further, the silicon-containing compound in the step (1) is at least one of ethyl orthosilicate, silicon acetate and methyl silicate;
further, the calcium salt in the step (1) is at least one of calcium nitrate, calcium chloride, calcium acetate and calcium citrate;
further, the magnesium salt in the step (1) is at least one of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium citrate;
further, the phosphorus salt in step (1) is at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Further, the mixed solution in the step (1) comprises the following components in parts by weight:
further, the time of the hydrolytic polycondensation reaction in the step (1) is 24-48 h.
Further, the pressure of the compression molding in the step (2) is 100-220MPa, and the time of the compression molding is 2-30 min;
preferably, the press-forming of step (2) comprises: filling zirconia powder into a plastic mould, sealing and molding by using an isostatic press.
Further, the temperature of the pre-sintering treatment in the step (2) is 500-; the rate of temperature rise is 2-10 ℃/min.
Further, the pore-forming agent in the step (3) is at least one of a polyethylacrylate microsphere, a polylactic acid-glycolic acid copolymer microsphere, a polyacrylic acid microsphere and a polystyrene microsphere, a polymethyl methacrylate microsphere and a graphite microsphere, and the particle size of the pore-forming agent is 1-20 μm;
further, the stabilizer in the step (3) is at least one of polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral and glycerol;
further, the dispersant in the step (3) is at least one of polyethylene glycol, polyacrylic acid and polymethacrylate ammonia;
further, the solvent in the step (3) is at least one of water and absolute ethyl alcohol.
Further, the suspension in the step (3) comprises the following components in parts by weight:
further, the drying temperature in the step (3) is 60-100 ℃, and the drying time is 6-12 h;
further, the thickness of the pore-forming surface layer in the step (3) is 10-80 μm;
preferably, the thickness of the pore-forming surface layer in the step (3) is 20-80 μm.
Preferably, the average pore diameter in the pore-forming surface layer in the step (3) is 0.1-50 μm, and the porosity is 20% -70%.
Further, the temperature of the sintering treatment in the step (3) is 1300-.
Preferably, the impregnating of step (3) comprises: and (3) soaking the zirconia ceramic pre-sintered body in zirconia suspension for 10s-2min, and quickly pulling out the zirconia ceramic pre-sintered body from the suspension 1 after soaking.
Preferably, the spraying of step (3) comprises: and spraying the suspension 1 on the zirconia ceramic pre-sintered body, wherein the spraying pressure is 0.2MPa, and the spraying time is 0.5-4 min.
Preferably, the zirconia powder in step (2) and step (3) is partially stabilized tetragonal zirconia powder with any one or more of Y2O3, MgO, CaO and La2O3 as a stabilizer.
Further preferably, the zirconia powder in step (2) and step (3) is yttria-stabilized zirconia powder.
Further, the infiltration pressure of the negative pressure infiltration treatment in the step (4) is 0-0.2 MPa, and the time of the negative pressure infiltration treatment is 10s-80 min;
further, the standing and aging time in the step (4) is 6-48 h; the drying temperature in the step (4) is 60-180 ℃, and the drying time is 12-72 h;
preferably, the temperature of the drying in step (4) is 60-100 ℃.
Further, the temperature of the heat treatment in the step (4) is 600-.
The invention provides a modified zirconia ceramic with a surface compounded with bioactive substances, which is prepared by the preparation method.
The invention permeates the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive sol into a zirconia pore canal with a porous surface layer structure, the sol is converted into gel after being dried at low temperature, then the sol is subjected to high-temperature heat treatment to generate calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances, and partial liquid phase or solid phase diffusion is generated in the high-temperature sintering process, so that certain bonding strength is ensured between the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances and zirconia, and the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances are embedded into the non-through pore canal, thereby ensuring that the bioactive substances cannot fall off from the pore canal and endowing the zirconia with high bioactivity.
In the preparation method provided by the invention, the sol is dried at low temperature and subjected to high-temperature heat treatment to generate the calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substances, and through controlling the composition and the heat treatment system of the sol, one or more of calcium-magnesium-silicon bioactive crystalline substances such as wollastonite, akermanite, diopside, whitlaite, and amesite or calcium-silicon-phosphorus bioactive glass substances can be generated, and the existence of the bioactive substances endows the zirconium oxide with high bioactivity. The porous surface layer structure and the zirconia ceramic are synchronously sintered, the materials are consistent, the problem of poor interface bonding strength of the surface active layer and the zirconia matrix material is solved, and the porosity, the pore size and the thickness of the porous surface layer structure can be regulated and controlled. The porous surface layer structure can permeate various active substances, is not limited by the types of the active substances, improves the dental ceramic repairing effect, promotes wider clinical application of the dental ceramic, and has certain social and economic values.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method provided by the invention, the porous zirconia layer is constructed on the surface of the zirconia ceramic with the compact structure for the first time, the thickness, the pore diameter and the porosity of the porous zirconia layer can be adjusted at will, the zirconia ceramic with the compact structure in the interior ensures that the dental ceramic has excellent mechanical strength, and the calcium, magnesium, silicon or calcium, silicon and phosphorus bioactive substances are loaded on the pore channel of the porous zirconia surface layer. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has a stimulating effect on the gene expression of osteoblasts, can obviously promote bone regeneration in clinical application, has a stimulating effect on the gene expression of osteoblasts, and can obviously promote bone regeneration in clinical application. The calcium-magnesium-silicon or calcium-silicon-phosphorus bioactive substance has good bioactivity, biocompatibility, biodegradability and mechanical properties, releases active ions such as calcium, magnesium, silicon, phosphorus and the like, can induce the formation of a apatite layer, and is beneficial to the combination of materials and bone tissues.
(2) After the modified zirconia dental ceramic with the surface compounded with the bioactive substances prepared by the invention is soaked in simulated body fluid for a period of time, weakly crystallized hydroxyapatite which is an inorganic substance in bone tissues can be mineralized on the surface, so that the bioactivity is obviously improved;
(3) the porous zirconia surface layer prepared by the invention can permeate various active sols without being limited by components and is not limited to one or more bioactive sols. The infiltration capacity of the bioactive sol can be adjusted by regulating the thickness, the pore diameter and the porosity of the porous surface layer of the zirconia, so that the bioactivity of the dental ceramic can be obviously improved;
(4) in the preparation method provided by the invention, the related zirconia ceramic surface modification treatment method is implemented on a presintered body formed and processed by zirconia ceramic, so that the problem of high processing difficulty of the sintered zirconia ceramic due to high hardness and high density is avoided, special equipment is not needed, the preparation method is simple, the yield is high, and the cost is low;
(5) compared with the problems that the bioactive coating prepared on the surface of a zirconia ceramic compact sintered body in the prior art is easy to peel off and dissolve in a complex oral environment due to poor interface bonding, the porous surface layer and the internal matrix of the zirconia ceramic with the porous surface layer are made of the same material, so that the prepared bioactive surface layer and the zirconia ceramic are an integrated material, the problem of residual stress caused by mismatch of thermal expansion coefficients is solved, the bioactive coating is more stably and firmly bonded with alveolar bone tissues, long-term stable bioactivity can be maintained, and the long-term clinical treatment effect is better.
Drawings
FIG. 1 is a cross-sectional microstructure result diagram of a modified zirconia ceramic with a surface compounded with a bioactive substance prepared in examples 1 to 4.
Fig. 2 is a surface microstructure result diagram of the modified zirconia ceramic surface-compounded with the bioactive substance according to example 1.
Fig. 3 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 1 after 7 days of simulated body fluid mineralization by SBF.
Fig. 4 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 2 after 7 days of simulated body fluid mineralization by SBF.
Fig. 5 is a graph showing the result of the microstructure of the modified zirconia ceramic with the surface compounded with bioactive substances of example 3 after 7 days of simulated body fluid mineralization by SBF.
FIG. 6 is a graph showing the results of co-culturing the modified zirconia ceramics with bioactive substances compounded on the surfaces thereof in examples 1 to 3, zirconia ceramics without any modification treatment, and mouse bone marrow mesenchymal stem cells for 1 day and 3 days.
FIG. 7 is a graph showing ALP quantification results of co-culture of the modified zirconia ceramics with bioactive substances compounded on the surfaces, which are obtained in examples 1 to 3, and zirconia ceramics without any modification treatment with mouse bone marrow mesenchymal stem cells for 7 days and 14 days.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
(1) Preparing the calcium-magnesium-silicon bioactive sol: adding 10g of ethyl orthosilicate, 20g of calcium nitrate and 30g of magnesium nitrate into 50g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing hydrolytic polycondensation reaction (the reaction time is 12 hours) to form calcium-magnesium-silica sol;
(2) pressing and molding yttria-stabilized zirconia powder at 220MPa for 2min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the speed of 10 ℃/min for 2h to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process, wherein the dipping time is 10s, the porous surface layer is dried for 12h at the temperature of 60 ℃ after the zirconia suspension is permeated and adsorbed, a pore-forming surface layer (the thickness is 10um) is formed, and then the sintering is carried out for 2h at the temperature of 1350 ℃ and the heating rate is 5 ℃/min, so as to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-magnesium-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol suspension is permeated into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive sol;
(6) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive sol prepared in the step (5) to 1300 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the bioactive substances.
Part a of fig. 1 is a cross-sectional microstructure result diagram of the modified zirconia ceramic surface-composited with bioactive substances prepared in example 1; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 10 μm.
Fig. 2 is a surface microstructure result diagram of the modified zirconia ceramic surface-compounded with the bioactive substance according to example 1. As can be seen from fig. 2, the pore size distribution of the porous surface layer is relatively uniform and the porosity is relatively high.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in the embodiment has high bioactivity, as shown in fig. 3, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is remarkably improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1100MPa, and the thickness of the surface porous layer is 10 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 2
(1) Preparing the calcium-magnesium-silicon bioactive sol: adding 10g of ethyl orthosilicate, 20g of calcium nitrate and 30g of magnesium citrate into 50g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and carrying out hydrolytic polycondensation reaction (the reaction time is 24 hours) to form calcium-magnesium-silica sol;
(2) pressing and molding yttria-stabilized zirconia powder under the pressure of 100MPa for 30min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment, wherein the presintering treatment time is 2h and the heating rate is 2 ℃/min to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the suspension at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10 mu m), and then sintering the surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-magnesium-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substance;
(7) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive sol prepared in the step (6) to 1300 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the calcium-magnesium-silicon bioactive substances.
Part b of fig. 1 is a cross-sectional microstructure result diagram of the modified zirconia ceramic with a surface-compounded bioactive substance prepared in example 2; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 15 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in the embodiment has high bioactivity, as shown in fig. 4, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is remarkably improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1050MPa, and the thickness of the surface porous layer is 15 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 3
(1) Preparing the calcium-silicon-phosphorus bioactive sol: adding 31g of ethyl orthosilicate, 29g of calcium nitrate and 20g of sodium phosphate into 20g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing a hydrolysis polycondensation reaction (the reaction time is 24 hours) to form calcium-silicon-phosphorus sol;
(2) pressing and molding yttria-stabilized zirconia powder at the pressure of 180MPa for 10min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the temperature of 2h and the heating rate of 5 ℃/min to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:10:2:53:25, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the porous surface layer at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10um), and sintering the pore-forming surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-silicon-phosphorus bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-magnesium-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substances;
(6) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-phosphorus-silicon bioactive sol prepared in the step (5) to 800 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the calcium-phosphorus-silicon bioactive substances.
Part c of FIG. 1 is a cross-sectional microstructure result diagram of the modified zirconia ceramic with a surface-compounded bioactive substance prepared in example 3; as can be seen from fig. 1, the porous surface layer is tightly bonded to the zirconia matrix, and the thickness of the porous surface layer is about 25 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in this example has high bioactivity, as shown in fig. 5, after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of the sample after the surface layer is permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is significantly improved.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1120MPa, and the thickness of the surface porous layer is 25 mu m by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Example 4
(1) Preparing the calcium-silicon-phosphorus bioactive sol: adding 31g of ethyl orthosilicate, 34g of calcium nitrate and 15g of sodium phosphate into 20g of deionized water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 8.0, and performing a hydrolysis polycondensation reaction (the reaction time is 24 hours) to form calcium-silicon-phosphorus sol;
(2) pressing and molding yttria-stabilized zirconia powder at the pressure of 200MPa for 10min to prepare a zirconia ceramic green body, and heating to 500 ℃ for presintering treatment at the temperature of 2h and the heating rate of 5 ℃/min to obtain a zirconia ceramic presintering body;
(3) preparation of zirconia suspension: mixing the polyethylacrylate microspheres, polyvinyl alcohol, polyacrylic acid, deionized water and zirconia powder according to the mass ratio of 10:5:2:53:30, uniformly mixing and stirring to prepare a suspension 1 (high-stability and high-dispersity zirconia suspension);
(4) dipping the suspension 1 prepared in the step (3) on the surface of the zirconia ceramic pre-sintered body prepared in the step (2) by a dipping and pulling process for 20s, drying the porous surface layer at 60 ℃ for 12h after the porous surface layer permeates and adsorbs the zirconia suspension to form a pore-forming surface layer (the thickness is 10um), and sintering the pore-forming surface layer at 1350 ℃ for 2h, wherein the temperature rising rate is 5 ℃/min to obtain the zirconia ceramic with the porous surface layer;
(5) soaking and permeating the zirconia ceramic with the porous surface layer prepared in the step (4) in the calcium-phosphorus-silicon bioactive sol prepared in the step (1) by a negative pressure permeation process, wherein the permeation pressure is 0.1MPa, the permeation time is 10s, so that the calcium-phosphorus-silicon bioactive sol permeates into the porous surface layer of the zirconia ceramic, taking out the zirconia ceramic, standing and aging the zirconia ceramic for 6h, and drying the zirconia ceramic at the temperature of 60 ℃ for 12h to obtain the zirconia ceramic with the porous surface layer compounded with the calcium-magnesium-silicon bioactive substance;
(6) and (3) heating the zirconia ceramic with the porous surface layer compounded with the calcium-phosphorus-silicon bioactive sol prepared in the step (5) to 900 ℃ for heat treatment for 0.5h, wherein the heating rate is 10 ℃/min, so as to obtain the modified zirconia ceramic (zirconia dental ceramic with high bioactivity and high strength) with the surface compounded with the calcium-phosphorus-silicon bioactive substances.
Part d of FIG. 1 is a cross-sectional microstructure result diagram of the surface-composite bioactive substance-modified zirconia ceramic prepared in example 4; as can be seen from FIG. 1, the surface porous layer was tightly bonded to the zirconia matrix, and the thickness of the porous layer was about 35 μm.
The modified zirconia ceramic with the surface compounded with the bioactive substances prepared in this embodiment has high bioactivity, and after the modified zirconia ceramic is soaked in 1.0 time of Simulated Body Fluid (SBF) for 8 days, abundant cluster-like crystals appear on the surface of a sample with the surface layer permeated with the calcium-magnesium-silicon bioactive sol, which indicates that the bioactivity of the modified zirconia ceramic is significantly improved, as shown in fig. 3-5.
The bending strength of the modified zirconia ceramic with the surface compounded with the bioactive substances is 1150MPa, and the thickness of the surface porous layer is 35um by mechanical property tests (refer to national standard GB/T6569-86). The preparation method provided by the embodiment of the invention improves the bioactivity to a certain extent on the premise of ensuring the excellent mechanical property of the product.
Cell experiments
Measuring proliferation of cells: under aseptic conditions, the modified zirconia ceramics with the surface compounded with the calcium, phosphorus and silicon bioactive substances prepared in the examples 1-3 and the zirconia ceramics without any modification treatment are sterilized at high temperature and high pressure and then dried to obtain zirconia ceramic samples (respectively marked as the example 1 sample, the example 2 sample, the example 3 sample and a blank group sample). Then putting each zirconia ceramic sample into a 48-pore plate respectively, soaking for 6h by using a complete culture medium, sucking away the complete culture medium, adding the mouse bone marrow mesenchymal stem cell suspension with the generation of 9 into the pore plate, wherein the number of cells in each pore is 10000, and the culture process is changed into the complete culture medium every other day. When the cells were cultured for 1d and 3d, the cells were assayed for expression of osteogenic differentiation alkaline phosphatase activity.
Determination of alkaline phosphatase expression: under aseptic conditions, the modified zirconia ceramics with the surface compounded with the calcium, phosphorus and silicon bioactive substances prepared in the examples 1-3 and the zirconia ceramics without any modification treatment are sterilized at high temperature and high pressure and then dried to obtain zirconia ceramic samples (respectively marked as the example 1 sample, the example 2 sample, the example 3 sample and a blank group sample). Then respectively putting each zirconia ceramic sample into a 48-pore plate, soaking for 6h by using a complete culture medium, sucking away the complete culture medium, adding mouse bone marrow mesenchymal stem cell suspension with the generation of 9 into the pore plate, wherein the number of cells in each pore is 20000, and replacing osteogenic induction liquid every other day in the culture process. When the cells were cultured for 7d and 14d, the cells were assayed for expression of osteogenic differentiation alkaline phosphatase activity.
The preparation of the zirconia ceramic without any modification treatment comprises the following steps: pre-sintering body of zirconia ceramic and calcining treatment. The zirconia ceramic pre-sintered body can be obtained by referring to step (2) of example 1, and then the zirconia ceramic pre-sintered body is subjected to a firing treatment, the firing treatment being: heating to 1300 deg.C for 0.5h at a heating rate of 10 deg.C/min.
FIG. 6 is a graph showing the results of co-culturing the modified zirconia ceramics with bioactive substances compounded on the surfaces thereof in examples 1 to 3, zirconia ceramics without any modification treatment, and mouse bone marrow mesenchymal stem cells for 1 day and 3 days.
As can be seen from fig. 6, the modified zirconia ceramic with a surface compounded with a bioactive substance prepared in the example and the mouse bone marrow mesenchymal stem cells were cultured together for 1 day and 3 days, and the cell proliferation effect was better than that of the zirconia ceramic without any modification treatment, and the cell proliferation condition was significantly improved.
At the time of 7 days and 14 days of co-culture, mouse bone marrow mesenchymal stem cells in each sample group were taken and detected using an ALP quantification kit. FIG. 7 is a graph showing ALP quantification results of co-culture of the modified zirconia ceramics with bioactive substances compounded on the surfaces, which are obtained in examples 1 to 3, and zirconia ceramics without any modification treatment with mouse bone marrow mesenchymal stem cells for 7 days and 14 days.
As can be seen from FIG. 7, the osteogenic differentiation effect of the cells of the modified zirconia ceramic with the surface compounded with the bioactive substances and the mouse bone marrow mesenchymal stem cells cultured together for 7 days and 14 days is better than that of the zirconia ceramic without any modification treatment, and the osteogenic differentiation condition of the cells is remarkably improved. Blank groups in fig. 6 and 7 show zirconia ceramics without any modification treatment, and 1, 2, and 3 show the example 1 sample, the example 2 sample, and the example 3 sample, respectively.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of modified zirconia ceramics with a surface compounded with bioactive substances is characterized by comprising the following steps:
(1) adding a silicon-containing compound, a calcium salt, a magnesium salt or a phosphorus salt into water, uniformly mixing to obtain a mixed solution, adjusting the pH of the mixed solution to 6.0-8.0, and performing hydrolytic polycondensation reaction to obtain calcium-magnesium silica sol or calcium-silicon-phosphorus sol;
(2) pressing and molding zirconia powder, heating to perform presintering treatment to obtain a zirconia ceramic presintering body;
(3) adding a pore-forming agent, a stabilizing agent, a dispersing agent and zirconia powder into a solvent, and uniformly mixing to obtain a suspension; dipping or spraying the suspension on the surface of the zirconia ceramic pre-sintered body in the step (2), drying to form a pore-forming surface layer, and heating for sintering treatment to obtain the zirconia ceramic with a porous surface layer;
(4) soaking the zirconia ceramic with the porous surface layer in the step (3) in the calcium-magnesium-silica sol or calcium-silicon-phosphorus sol prepared in the step (1), performing negative pressure infiltration treatment, taking out, standing for aging, and drying to obtain the zirconia ceramic with the composite surface layer; and heating the zirconia ceramic with the surface layer compounded for heat treatment to obtain the modified zirconia ceramic with the surface compounded with the bioactive substances.
2. The method for preparing the surface-composite bioactive substance-modified zirconia ceramic according to claim 1, wherein the silicon-containing compound in the step (1) is at least one of tetraethoxysilane, silicon acetate and methyl silicate; the calcium salt in the step (1) is at least one of calcium nitrate, calcium chloride, calcium acetate and calcium citrate; the magnesium salt in the step (1) is at least one of magnesium nitrate, magnesium chloride, magnesium acetate and magnesium citrate; the phosphorus salt in the step (1) is at least one of sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
3. The method for preparing a modified zirconia ceramic with a surface compounded with a bioactive substance according to claim 1, wherein the mixed solution in the step (1) comprises the following components in parts by weight:
4. the method for preparing the surface-modified zirconia ceramic with a bioactive substance compounded thereon according to claim 1, wherein the time of the hydrolytic polycondensation reaction in the step (1) is 24 to 48 hours.
5. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances as claimed in claim 1, wherein the pressure for the compression molding in the step (2) is 100-220MPa, and the time for the compression molding is 2-30 min; the temperature of the pre-sintering treatment is 500-1000 ℃, and the time of the pre-sintering treatment is 0.5-3 h; the rate of temperature rise is 2-10 ℃/min.
6. The method for preparing the surface-modified zirconia ceramic with a composite bioactive substance according to claim 1, wherein the pore-forming agent in step (3) is at least one of polyethylacrylate microspheres, polylactic acid-glycolic acid copolymer microspheres, polyacrylic acid microspheres and polystyrene microspheres, polymethyl methacrylate microspheres, and graphite microspheres, and the particle size of the pore-forming agent is 1-20 μm; the stabilizer in the step (3) is at least one of polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl butyral and glycerol; the dispersant in the step (3) is at least one of polyethylene glycol, polyacrylic acid and polymethacrylate ammonia; and (3) the solvent is at least one of water and absolute ethyl alcohol.
7. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to claim 1, wherein the suspension in the step (3) comprises the following components in parts by mass:
8. the method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to claim 1, wherein the drying temperature in the step (3) is 60-100 ℃, and the drying time is 6-12 h; the thickness of the pore-forming surface layer in the step (3) is 20-80 μm; the sintering treatment temperature in the step (3) is 1300-1600 ℃, the sintering treatment time is 2-4h, and the heating rate is 2-10 ℃/min.
9. The method for preparing the modified zirconia ceramic with the surface compounded with the bioactive substances according to the claim 1, characterized in that the infiltration pressure of the negative pressure infiltration treatment in the step (4) is 0-0.2 MPa, and the time of the negative pressure infiltration treatment is 10s-80 min; the standing and aging time of the step (4) is 6-48 h; the drying temperature in the step (4) is 60-180 ℃, and the drying time is 12-72 h; the temperature of the heat treatment in the step (4) is 600-1300 ℃, the time of the heat treatment is 0.5-4h, and the heating rate is 2-10 ℃/min.
10. A modified zirconia ceramic with a surface compounded with a bioactive substance, which is prepared by the preparation method according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114767927A (en) * | 2022-04-02 | 2022-07-22 | 华南理工大学 | Silicon/zinc ion doped biphase calcium phosphate ceramic bracket and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030180518A1 (en) * | 2000-03-29 | 2003-09-25 | Dirk Rogowski | Sintered shaped body, whose surface comprises a porous layer and a method for the production thereof |
| CN1665551A (en) * | 2002-06-27 | 2005-09-07 | 内用假肢股份公司 | Open-pored metal coating for joint replacement implants and method for production thereof |
| US20080213725A1 (en) * | 2003-09-24 | 2008-09-04 | Nobel Biocare Ab (Publ) | Method and Arrangement for a Dental Installation |
| CN108285343A (en) * | 2018-01-15 | 2018-07-17 | 华南理工大学 | A kind of preparation method of bioactivity glass coating modification zirconium oxide dental porcelain |
| CN109180182A (en) * | 2018-08-28 | 2019-01-11 | 西安交通大学 | A kind of zirconium oxide artificial tooth and its photocuring dynamic molding method with gradient mechanical property |
-
2021
- 2021-05-08 CN CN202110502544.8A patent/CN113248278B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030180518A1 (en) * | 2000-03-29 | 2003-09-25 | Dirk Rogowski | Sintered shaped body, whose surface comprises a porous layer and a method for the production thereof |
| CN1665551A (en) * | 2002-06-27 | 2005-09-07 | 内用假肢股份公司 | Open-pored metal coating for joint replacement implants and method for production thereof |
| US20080213725A1 (en) * | 2003-09-24 | 2008-09-04 | Nobel Biocare Ab (Publ) | Method and Arrangement for a Dental Installation |
| CN108285343A (en) * | 2018-01-15 | 2018-07-17 | 华南理工大学 | A kind of preparation method of bioactivity glass coating modification zirconium oxide dental porcelain |
| CN109180182A (en) * | 2018-08-28 | 2019-01-11 | 西安交通大学 | A kind of zirconium oxide artificial tooth and its photocuring dynamic molding method with gradient mechanical property |
Non-Patent Citations (2)
| Title |
|---|
| DAWLAT MOSTAFA: "Bioactive-hybrid-zirconia implant surface for enhancing osseointegration: an vivo study", 《INTERNATIONAL JOURNAL OF IMPLANT DENTISTRY》 * |
| 王莉丽: "羟基磷灰石/氧化锆生物复合材料制备与性能研究", 《中国优秀博硕士学位论文全文数据库(博士)工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114767927A (en) * | 2022-04-02 | 2022-07-22 | 华南理工大学 | Silicon/zinc ion doped biphase calcium phosphate ceramic bracket and preparation method thereof |
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