CN108530064A - 基于氧化锆的复合材料 - Google Patents
基于氧化锆的复合材料 Download PDFInfo
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- CN108530064A CN108530064A CN201810480072.9A CN201810480072A CN108530064A CN 108530064 A CN108530064 A CN 108530064A CN 201810480072 A CN201810480072 A CN 201810480072A CN 108530064 A CN108530064 A CN 108530064A
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 229910001928 zirconium oxide Inorganic materials 0.000 title claims abstract description 58
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003381 stabilizer Substances 0.000 claims description 19
- 230000006378 damage Effects 0.000 claims description 18
- 239000005084 Strontium aluminate Substances 0.000 claims description 11
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007943 implant Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- 125000006850 spacer group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 238000002513 implantation Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 35
- 238000005245 sintering Methods 0.000 description 21
- 239000011521 glass Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 230000006641 stabilisation Effects 0.000 description 18
- 239000013078 crystal Substances 0.000 description 15
- 238000011105 stabilization Methods 0.000 description 15
- 238000012545 processing Methods 0.000 description 12
- 229910052907 leucite Inorganic materials 0.000 description 10
- 239000002241 glass-ceramic Substances 0.000 description 8
- -1 oxonium ion Chemical class 0.000 description 8
- 230000035882 stress Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 239000010433 feldspar Substances 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000002002 slurry Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 229910052845 zircon Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001513 hot isostatic pressing Methods 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000011351 dental ceramic Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910001649 dickite Inorganic materials 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 229940077441 fluorapatite Drugs 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing 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
- 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 2
- 229910052903 pyrophyllite Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 206010006514 bruxism Diseases 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000002670 dental porcelain Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- C04B35/4885—Composites with aluminium oxide
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- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
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- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
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Abstract
本发明涉及基于氧化锆的复合材料。具体地,本发明涉及一种含氧化锆基质的陶瓷复合材料以及其制备方法。
Description
本专利申请是申请号为201380054517.2,申请日为2013年8月20日,优先权日为2012年8月20日,同题的发明专利申请的分案申请。
技术领域
本发明涉及一种陶瓷复合材料、其制备和应用。本发明特别涉及一种基于氧化锆的复合材料,一种均匀多相的生物相容的多晶陶瓷。
背景技术
该基于氧化锆的复合材料可在牙科领域用于制备齿桥和齿冠,例如用于制备牙植入体,用于制备医学工程构件如脊柱植入体,但通常也可用于需要具有无损硬质加工性的工程陶瓷的领域,例如在机加工如切削、铣和钻的过程中。
陶瓷材料由于其耐化学性、机械和物理特性以及可产生优异美学的光学特性,在牙科市场优于常规金属材料。
牙科用陶瓷的总趋势是朝向“全陶瓷体系”的方向。但目前仍常将陶瓷作为镶面施加在金属支架上。牙科用陶瓷可按其制备方法及其结晶相加以分类。
金属-陶瓷体系自1960年就存在。为获得仿照天然牙齿的美学上可接受的修复,在金属支架上施加镶面陶瓷。典型的镶面材料由通常基于白榴石晶体的长石玻璃构成。在长石玻璃结构中加入石榴石晶体 (KAlSi2O6) 可在支架和镶面的热膨胀系数方面导致最佳特性。白榴石晶体通过在1150-1530℃之间的温度下的天然长石的不一致熔融而形成。通过改变玻璃中的白榴石晶体含量可有针对性地控制热膨胀系数并适配于该金属支架。在长石玻璃中典型的白榴石晶体含量通常为15-25 体积%。因此该热膨胀系数小于金属的热膨胀系数,并可在压力下安装所施加的镶面。该镶面陶瓷通常在真空下烧结,以减少最终产品中的孔隙度。该基于白榴石晶体的玻璃 (也称为牙科用瓷) 由于该玻璃相,其机械特性在牙医学中所用的全部陶瓷材料中是最低的。直到2005年,所有牙修复的50 %仍用金属-陶瓷体系制备。
全陶瓷体系是不含金属的,并自30年来已可供使用。该工艺技术在不断发展 (如热压制法、浆料浇注法、CAD/CAM加工法)。与金属-陶瓷体系的主要差别在于具有高得多的结晶相含量,该结晶相含量可在35-100 体积%之间。机械性能有所改进,但不透明性也增加,这在所需的美学方面是不利的。
存在多种对全陶瓷体系的耐用性具有影响的因素,如口腔环境、从酸至碱的波动的pH-值、循环负荷和咀嚼期间的最大负荷峰。具有较高玻璃含量的全陶瓷体系的失效原因经常是应力裂纹腐蚀。由于Y-TZP-陶瓷 (100体积% 结晶相,Y-稳定的四方氧化锆) 在低温下的水热老化,因此要求按标准进行测试,在该标准中要评定在人类环境中和在循环负荷下的耐用性。
全陶瓷体系主要根据制备方法分类 (例如热压制、干式压制和烧结、浆料浇注、CAD/CAM加工)。在热压制中,首先使用具有35-45体积% 的结晶相比例的基于白榴石晶体的玻璃。其机械性能比金属-陶瓷体系的基于白榴石晶体的玻璃高一倍。多次加热可有利于白榴石结晶作用,并导致更高的强度。
对热压制现今使用新型的玻璃陶瓷。该材料由具有65体积% 的结晶相比例的基于二硅酸锂的玻璃组成。伦琴射线研究表明,除二硅酸锂 (Li2Si2O5)外还有其它的晶相如硅酸锂 (Li2SiO3) 和方英石 (SiO2)。与基于白榴石晶体的玻璃相比,该机械性能再高一倍。
全陶瓷体系的干式压制和烧结自90年代初已使用。该制备以计算机辅助进行,并考虑了烧结时压制生坯的烧结收缩。使用基于氧化铝和基于氧化锆的陶瓷 (100体积% 结晶相比例)作为骨架材料,在其上另外施加由玻璃陶瓷制成的镶面。氧化铝陶瓷的特征在于约600 MPa的抗弯强度和优异的体内特性。
自90年代起已使用浆料浇注法。其中借助于结晶相的浆料浇注制备多孔生坯体,接着进行烧结和渗入基于镧的玻璃。
在牙科市场中可得到下列玻璃陶瓷:
氧化铝 (Al2O3)、尖晶石 (MgAl2O4) 或12Ce-TZP/Al2O3-组合物。该渗入玻璃的氧化铝的机械特性与基于二硅酸锂的玻璃陶瓷相当,但具有最少更高的不透明性。该经渗入玻璃的尖晶石具有明显更高的半透明性,并且机械特性与基于二硅酸锂的玻璃陶瓷相当。在所有浆料浇注的牙科用陶瓷中,该渗入玻璃的氧化锆/氧化铝-组合物显示出最高的强度和断裂韧性。
70年代初期以来,实施了计算机控制的CAD/CAM加工陶瓷块料或坯料,并曾由Duret引入。那时是对密烧结的坯料进行加工。现今主要用预烧结的坯料加工。
由于玻璃陶瓷的非常好的可加工性,其适用于密烧结状态的CAD/CAM加工。更早基于理想的可加工性而使用典型的基于云母晶体的玻璃。现今使用具有透长石晶体、白榴石晶体或二硅酸锂晶体的长石玻璃。但对密烧结的玻璃陶瓷的CAD/CAM加工显示出明显的工具磨损。表面缺陷可对体内特性产生不利影响。
玻璃陶瓷通常可非常好地进行加工。由于晶体和玻璃基质不同的热膨胀系数,在冷却时沿相界面会产生微裂纹。此外,该结晶相具有非常好的沿纵向 (特别是沿晶体学(001)面的云母) 的可劈性。该晶相不应具有优选取向,即在玻璃结构中各向同性地分布。由工具造成的裂纹沿劈面或也沿晶体和玻璃基质之间的相界面延伸。由此,在加工时不断使该裂纹转向,并且仅表面上小的区域从工件剥落。
自2001年以来,实现了对预烧结的氧化锆-坯料的CAD/CAM加工。该加工较容易、较快,并显示出比必须加工密烧结的块料时更小的工具磨损。但接着必须密烧结该加工完的工件。伴随尺寸偏差出现的烧结收缩中的波动以及由牙科技师手工修正加工导致氧化锆增加的受损风险。
作为支架材料的氧化锆具有至今最好的机械特性。但由于在支架和镶面之间的界面上额外需要的镶面陶瓷,经常会通过该四方氧化锆相的相变而出现裂纹。一段时间以来,已有多个已公开的3-年-体内-研究和5-年-体内-研究。这些研究的结果是优异的成功率,但具有低的存活率并伴随并发症如龋齿病或镶面剥落。实际的研发趋势明确地朝向氧化锆/氧化铝-复合材料,目的是改进抗水热老化性和机械特性。
发明内容
本发明的目的在于,避免现有技术的缺点和特别是提供一种陶瓷,其机械特性允许进行无损硬质加工和/或具有好的抗水热老化性。此外,该陶瓷应可用常规方法制备和加工。本发明的目的借助于权利要求1的复合材料和权利要求15的所属方法实现。
相对于现有技术,本发明的新型材料的优点可基于改进的“损伤容限”定量测定。损伤容限是一种机械特征值,其描述了材料对外部施加的损伤的抗力。在实际中该损伤可由于用镶有金刚石的工具的研磨处理而发生。
为在实验室中测量损伤容限,借助于金刚石针尖 (维氏硬度计)在规定的应力下对试样体施加损伤。在硬度压痕的区域内形成裂纹,以致该试样体在此部位受到削弱。通过测量该部位的残余-断裂应力或残余强度定量测算该削弱。在规定的削弱后的残余强度越高,则该材料的损伤容限越大。
为详细地描述损伤容限,在一系列的试样体上以不同的应力施加损伤。由此得出该工件的特性曲线 (残余强度对应力)。材料相对于现有技术改进的损伤容限是通过比较这些特性曲线证实的,参见图7和8。
本发明涉及制备和应用基于氧化锆的复合材料,特别是适于在密烧结状态的无损硬质加工的复合材料。本发明的复合材料借助于本身己知的常规陶瓷技术制备。主要的工艺步骤例如是:
a) 将预先确定组成的粉末混合物置入水中;任选使用液化器/剂以避免沉降
b) 在溶解器 (高速运行的搅拌器) 中匀化
c) 在搅拌式球磨机中研磨,以此提高粉末混合物的比表面积(=粉碎和匀化)
d) 任选加入有机粘合剂
e) 喷雾干燥,由此产生具有给定特性的可流动的颗粒物
f) 用水和任选另外的助压剂润湿颗粒物
g) 轴向压制块料
h) 切削加工坯料状态或预烧结状态的块料,由此在考虑烧结收缩的情况下在很大程度上塑造出最终轮廓
i) 烧结 (这也可以以3-步烧结进行:预烧到约97% 的理论密度。向外闭合仍保留的残余孔。在高温和高气体压力下热等静压制 (HIP),由此实际上完全最终压实。所谓的强化焙烧,由此以补偿在热等静压制中所产生的陶瓷中的氧离子的不平衡)
j) 通过用镶有金刚石的工具进行研磨和抛光的硬质加工。
本发明的复合材料例如可用于制备烧结型体,用于制备人造假牙、牙修复如齿桥、齿冠、嵌体(Inlay)和高嵌体(Onlay),用于制备牙根桩(Zahnwurzelstiften)、植入体和基牙(Abument)。优选用于植入体技术领域。特别优选用于脊柱领域如间隔件(Spacer)/鸟笼式螺纹固定器(Cage)。
该基于氧化锆的复合材料具有氧化锆作为陶瓷基质和分散在其中的至少一个二次相或分散体和任选的添加剂。该复合材料包含至少51体积%的氧化锆比例作为第一相和比例为1-49体积% 的二次相和任选的一种或多种无机添加剂。基于总氧化锆比例计,氧化锆的主要部分,优选90-99体积%,特别优选95-99体积%以四方相存在,其中氧化锆的四方相的稳定化有时不仅在化学上而且在机械上实现。本文中的术语“二次相”和“分散体”作为同义词使用。
除化学稳定化而外还具有机械稳定化的呈四方相的氧化锆能够有利地实现与现有技术相比降低化学稳定剂的含量。
由ZTA-复合材料 (氧化锆增韧的氧化铝) 已知呈四方相的氧化锆的机械稳定化。那里认为,机械稳定化一方面受氧化锆粒度的影响。在氧化铝-复合材料中该粒度不应大于0.5 µm,按截线法测定。另一方面认为,各氧化锆颗粒嵌入氧化铝-基质中具有机械稳定化的主要部分,其中认为65体积% 的氧化铝最低含量是必需的,优选更高含量。
由本发明可证实,氧化锆的这种机械稳定化不仅在将氧化锆作为分散体相填入氧化铝中时起作用,而且在主要由氧化锆构成的陶瓷中也起作用。根据本发明加入二次相/分散体补偿了在氧化锆的四方晶体结构转变成单斜晶体结构时所出现的膨胀,由此没有产生必然的宏观裂纹,就能实现在其它较刚性的陶瓷结构中的在微晶-平面上的微移动/微剪切。
此外,机械稳定化也意指,氧化锆的四方相通过整体结构中的机械应力而稳定。在烧结工艺后冷却时,ZrO2和二次相的不同热膨胀系数会引起这些应力。
因此,该机械稳定化是特别有利的,因为其导致需较少份量的用于化学稳定化的化合物。化学稳定化基于氧化锆-离子被在晶格中产生氧空位并由此具有较小“空间需求”的阳离子部份取代。但是,在晶格中的氧空位可能是水热老化的侵蚀点。因此,同时至少降低化学稳定化的必要性的机械稳定化导致该复合材料具有改进的抗水热老化的稳定性。
按本发明的一个优选实施方案,该氧化锆基质的粒度平均为0.1-2.0 µm,特别优选平均为0.5-2.0 µm。按本发明的一个扩展方案,本发明的复合材料中的化学稳定剂的比例 (各自相对于氧化锆含量计的比例) 为:Y2O3 ≤ 3 mol %,优选≤ 2.5 mol %;CeO2 ≤12 mol %;Gd2O3 ≤ 3 mol %;Sm2O3 ≤ 3 mol %和Er2O3 ≤ 3 mol %。本发明复合材料中的化学稳定剂包括一种或多种所提及的添加剂,其中优选Y2O3。化学稳定剂的总含量相对ZrO2-含量计有利地为 < 12 mol %。
按一个实施方案,该氧化锆和分散体可含可溶性组分。可溶性组分可以是例如Cr、Fe、Mg、Ca、Ti、Y、Ce、镧系元素和/或V。这些组分一方面可起着色添加剂的作用和另一方面起烧结助剂的作用。这些组分通常作为氧化物加入。
所述二次相或分散体的颗粒大小优选不明显大于氧化锆基质的粒度。其优选为0.2-2.0 µm,特别优选为0.2-0.5 µm。该二次相或分散体的体积比例明显小于氧化锆的该比例。其为总体积的最多49体积%,优选1-10体积%,特别优选4-6体积%。该二次相是化学稳定的,并在高温下通过烧结制备该复合材料时不溶解于氧化锆中。
可使用下列化合物作为二次相或分散体:铝酸锶 (SrAl12O19)、铝酸镧(LaAl11O18)、羟基磷灰石 (Ca10(PO4)6(OH)2)、氟磷灰石 (Ca10(PO4)6F2)、磷酸三钙 (Ca3(PO4)2)、尖晶石 (MgAl2O4)、氧化铝 (Al2O3)、钇-铝-石榴石 (Y3Al5O12)、富铝红柱石(Al6Si2O13)、锆石 (ZrSiO4)、石英 (SiO2)、滑石 (Mg3Si4O10(OH)2)、高岭石 (Al2Si2O5(OH)4)、叶蜡石 (Al2Si4O10(OH)2)、钾长石 (KAlSi3O8)、白榴石 (KAlSi2O6)和硅酸锂(Li2SiO3)。优选铝酸锶、铝酸镧、羟基磷灰石、氟磷灰石、尖晶石、氧化铝和锆石;特别优选铝酸镧、氟磷灰、尖晶石和氧化铝。
该二次相或分散体可在微观平面上产生非弹性微变形。由于其晶体结构,该微变形可在微观平面上产生剪切变形。
按本发明的一个特别优选的实施方案,该二次相不是在烧结时才形成,而是用于制备该陶瓷的起始物质的一部分。
该复合材料的抗断强度优选 ≥ 800 MPa。
令人意外地已表明,该二次相或分散体可明显降低该复合材料的硬度。同时令人意外地也已表明,化学稳定剂的种类对该复合材料的硬度有明显影响。
此外也已令人意外地表明,该复合材料的断裂韧性、硬度和损伤容限也受该二次相或分散体的种类和量以及受化学稳定剂的种类的影响。
附图说明
图1示出含和不含本发明的分散体和各自具有不同化学稳定剂的实验系列的结果。
图2示出本发明的复合材料中使用不同分散体的实验系列。
图3示出具有本发明的分散体和该分散体相的不同含量 (体积%) (x-轴31) 的多个实验系列。
图4示出表明化学稳定剂对纯氧化锆材料和本发明的复合材料的影响的实验系列。
图5示出含不同分散体的实验系列,并示出其对本发明的复合材料的断裂韧性(y-轴50) 的影响。
图6示出含分散体和具有该分散体相的不同含量的本发明复合材料的多个实验系列。
图7示出用Y-稳定化和以六铝酸锶作为二次相的本发明的复合材料。
图8示出不同材料体系,即ZTA- (氧化锆增韧的氧化铝) 82、Y-TZP- (Y-稳定的多晶氧化锆) 83和本发明的复合材料 (六铝酸锶增韧的氧化锆) 84在不同的损伤 (这里指维氏硬度-压痕) 后的残余强度值。
具体实施方式
下面借助实验系列阐述本发明,但非由此限制本发明:
实验系列1:硬度与化学稳定剂的关系
图1示出含和不含本发明的分散体和各自具有不同化学稳定剂的实验系列的结果。在X-轴11上是所用分散体相的量和种类,即不含分散体且用Y2O3-稳定化的氧化锆13或用CeO2-稳定化的氧化锆14,含15体积% 的六铝酸锶-分散体且用Y2O3-稳定化的氧化锆15或用CeO2-稳定化的氧化锆16和含30体积% 的Al2O3-分散体且用Y2O3-稳定化的氧化锆17或用CeO2-稳定化的氧化锆18与y-轴10上的维氏硬度HV10的关系。
曾对化学稳定剂氧化钇 (Y2O3) 和氧化铈 (CeO2) 进行了试验。在此令人意外地证实,与用Y-稳定化的方案13, 15, 17相比,所有用Ce-稳定化的方案具有明显较低的硬度值。该硬度是以98.07 N的力借助于维氏硬度压痕 (HV10) 推算的。
由Ce-稳定的纯氧化锆具有最低的硬度即800 (HV10)。鉴于本发明在牙科领域的应用,较低的硬度是所期望的。在臼齿区域,由经常使用的Y-TZP制成的人造假牙会碰到天然牙齿。Y-TZP的硬度约为1250 (HV10)。天然牙齿或牙釉质由于渗入的羟基磷灰石晶体而具有明显更低的硬度即约400 (HV10)。该硬度差例如可在应激引起的摩擦移动 (磨牙症)时导致天然牙齿的显着磨损。由此原因,本发明的复合材料的较低硬度是有针对性的。此外,该复合材料的较低硬度还可导致无损硬质加工 (例如在研磨咬合架中的人造牙齿时)。
实验系列2:硬度与分散体种类的关系
图2示出本发明的复合材料中使用不同分散体的实验系列。在该实验系列中,仅相互对比在复合材料中具有相同分散体相比例 (5体积%) 的方案。在y-轴20上给出维氏硬度HV10。x-轴21示出各含5体积% 分散体的氧化锆 (SrAl12O19 23, 23a、MgAl2O4 24, 24a、SiO2 25、ZrSiO4 26、Al6Si2O13 27、Al2Si2O5(OH)4 28),并与不含分散体的22, 22a相比较。用Y2O3-稳定化的方案22, 23, 24, 25, 26, 27和28对所有组合物进行了检验,此外,用CeO2-稳定化的方案22a,23a对用六铝酸锶和尖晶石作为分散体的氧化锆-复合材料进行了检验。
令人意外地表明,通过加入分散体可影响硬度。同样也表明,该影响程度与分散体相的组成有关。
实验系列3:硬度与分散体相含量的关系
图3示出具有本发明的分散体和该分散体相的不同含量 (体积%) (x-轴31) 的多个实验系列。在Y-稳定的氧化锆中对氧化铝 (Al2O3) 32、羟基磷灰石 (Ca10(PO4)6(OH)2) 34和六铝酸锶 (SrAl12O19) 33进行了检验和在Ce-稳定的氧化锆中对尖晶石 (MgAl2O4) 进行了检验。
在此令人意外地已证明,画在y-轴30上的维氏硬度可明显受分散体相的含量的影响。该复合材料的硬度通常由所涉及的组分各自硬度的百分比混合得出。在该实验系列中令人意外地表明,这种混合规则并不总是适用。通过在Y-稳定的氧化锆中引入15体积% 的羟基磷灰石34可使硬度从约1250降到约1050 (HV 10)。通过引入5体积% 的铝酸锶33可使Y-稳定的氧化锆的硬度从1250降到约1210 (HV 10)。
实验系列4:断裂韧性与化学稳定剂的关系
图4示出表明化学稳定剂对纯氧化锆材料和本发明的复合材料的影响的实验系列。在x-轴上给出含各分散体相的材料,即纯氧化锆42, 43,含25体积% 六铝酸锶作为分散体相的氧化锆44, 45和含30体积% Al2O3作为分散体相的氧化锆46, 47,各含Y2O3 42, 44, 46作为化学稳定剂和各含CeO2 43, 45, 47作为化学稳定剂。
令人意外地表明,使用氧化铈 (CeO2) 作为化学稳定剂明显提高了纯材料43和复合材料45, 47的断裂韧性 (y-轴40)。本发明方案的断裂韧性可按维氏硬度压痕推算。高韧性方案如Ce-稳定的纯氧化锆43在硬度压痕时未产生裂纹。由此原因,在图4中15 MPa*m0.5的断裂韧性值是通过高韧性方案的外推法求取的。
实验系列5:断裂韧性与分散体相的关系
图5示出含不同分散体的实验系列,并示出其对本发明的复合材料的断裂韧性 (y-轴50) 的影响。在x-轴51上绘出纯氧化锆材料52, 52a、含六铝酸锶作为分散体相的氧化锆53, 53a、含尖晶石作为分散体相的氧化锆54a、含石英作为分散体相的氧化锆55、含锆石作为分散体相的氧化锆56、含富铝红柱石作为分散体相的氧化锆57和含高岭石作为分散体相的氧化锆58,部分用Y2O3-稳定化52, 53, 55, 56, 57, 58和部分用CeO2-稳定化52a, 53a,54a。
令人意外地表明,将分散体相加入到Ce-稳定的复合材料中对断裂韧性无影响。
相反,令人意外地表明,将分散体相加入到Y-稳定的复合材料中有时对断裂韧性产生明显影响。通过将铝酸锶 (SrAl12O19) 作为分散体相加入到复合材料53中,其断裂韧性可从5.3 MPa*m0.5明显提高到12.3 MPa*m0.5。
实验系列6:断裂韧性与分散体相含量的关系
图6示出含分散体和具有该分散体相的不同含量的本发明复合材料的多个实验系列。在x-轴61上以体积% 给出分散体相的含量在y-轴60上绘出单位为MPa*m0.5的断裂韧性。
在Y-稳定的氧化锆中检测氧化铝 (Al2O3) 62和铝酸锶 (SrAl12O19) 并在Ce-稳定的氧化锆中检测尖晶石 (MgAl2O4) 。令人意外地表明,相关于所用的分散体,就好的断裂韧性而言在本发明的复合材料中的分散体相的含量存在最佳值。在本发明的复合材料中,对于铝酸锶作为分散体相而言的最佳值为1-15体积%。
实验系列7:损伤容限与分散体相含量的关系
图7示出用Y-稳定化和以六铝酸锶作为二次相的本发明的复合材料。在x-轴71上借助其二次相-含量 (体积%) 表征不同的复合材料。在y-轴70上给出在HV50-损伤后该复合材料的残余强度 (MPa)。所试验的复合材料的标号为72。
明显地表明,与其它检验材料相比,铝酸锶-含量为5-15体积% 和特别是含5体积%的二次相的复合材料72提高了该复合材料的残余强度数倍。
实验系列8:与现有技术的材料相比的该复合材料的损伤容限
图8示出不同材料体系,即ZTA- (氧化锆增韧的氧化铝) 82、Y-TZP- (Y-稳定的多晶氧化锆) 83和本发明的复合材料 (六铝酸锶增韧的氧化锆) 84在不同的损伤 (这里指维氏硬度-压痕) 后的残余强度值。该检验的压痕负荷以对数N示于x-轴81上,相对于y-轴80上绘出的残余强度 (MPa)。
与现有技术的材料相比表明,该新型复合材料在不变的起始强度情况下,在不同损伤负荷后显示出明显更高的损伤容限。
下面再次总结本发明的复合材料的优点:
• 借助于已知的常规陶瓷技术制备本发明的复合材料
• 3-步烧结 (预烧、HIP、强化焙烧),由此产生较高的强度
• 通过使用CeO2作为化学稳定而无水热老化
• 通过较少比例的Y2O3作为化学稳定产生明显减少的水热老化,这是由于机械的部分稳定化或额外加入对抗老化无不利影响的其它化学稳定剂实现的
• 高的损伤容限
• 低风险的硬质加工
• 较低的硬度
• 本发明的复合材料在牙技术或牙科领域中用于制备适于以预烧结或密烧结状态CAD/CAM-加工的坯料或块料,制备适于假牙、牙修复 (齿桥、齿冠、嵌体、高嵌体) 的坯料或块料的应用
• 优选用作牙根桩、植入体、基牙以及其它应用
• 特别优选作为脊柱植入体 (例如间隔件/鸟笼式螺纹固定器)。
Claims (13)
1.复合材料,其包括氧化锆陶瓷基质和分散于其中的至少一个二次相,其特征在于,所述氧化锆基质在所述复合材料中的比例为至少51体积%,和所述二次相在所述复合材料中的比例为1-10体积%,其中基于氧化锆总比例计,主要部分的氧化锆以四方相存在,并且所述氧化锆的四方相是化学和/或机械稳定的,和所述二次相选自一种或多种下列化合物:六铝酸锶 (SrAl12O19)和钇-铝-石榴石 (Y3Al5O12)。
2.根据权利要求1的复合材料,其特征在于,所述氧化锆基质具有平均0.1-2.0 µm,优选平均0.5-2.0 µm的粒度。
3.根据权利要求1或2之一的复合材料,其特征在于,含有Y2O3 、CeO2 、Gd2O3、Sm2O3 和/或Er2O3 作为化学稳定剂,其中基于氧化锆含量计,化学稳定剂的总含量< 12 mol %。
4.根据权利要求3的复合材料,其特征在于,分别基于氧化锆-含量计,Y2O3的含量 ≤ 3mol %,优选≤ 2.5 mol % 和/或CeO2的含量≤ 12 mol % 和/或Gd2O3的含量 ≤ 3 mol %和/或Sm2O3的含量 ≤ 3 mol % 和/或Er2O3的含量 ≤ 3 mol %。
5.根据前述权利要求之一的复合材料,其特征在于,所述氧化锆和/或二次相含有可溶性组分。
6.根据权利要求5的复合材料,其特征在于,包含一种或多种下列元素,优选作为氧化物,作为可溶性组分:Cr、Fe、Mg、Ca、Ti、Y、Ce、镧系元素和/或V。
7.根据前述权利要求之一的复合材料,其特征在于,所述二次相的颗粒大小小于或等于所述氧化锆的粒度,其中所述颗粒大小优选为0.2-2.0 µm,特别优选0.2-0.5 µm。
8.根据前述权利要求之一的复合材料,其特征在于,所述二次相在所述复合材料中的比例为4-6体积%。
9.根据前述权利要求之一的复合材料,其特征在于,所述复合材料的硬度 < 1350(HV10),优选 < 1200,和特别优选 < 1000。
10.根据前述权利要求之一的复合材料,其特征在于,所述复合材料的抗断强度 ≥800 MPa。
11.根据前述权利要求之一的复合材料,其特征在于,HV50-压痕后的损伤容限或残余强度 > 400 MPa,优选 > 500 MPa,和特别优选 > 600 MPa。
12.根据前述权利要求之一的复合材料在牙科技术或医学技术中,特别是在制造人工假牙、牙修复如齿桥、齿冠、嵌体和高嵌体、牙根桩、植入体和基牙中,优选在植入体技术领域中,特别优选在脊柱领域如间隔件/鸟笼式螺纹固定器中的应用。
13.由根据权利要求1-11之一的复合材料制造烧结型体的方法,所述方法包括下列步骤:
a) 将预先确定组成的粉末混合物置入水中;任选使用液化器/剂,
b) 在溶解器 (高速运行的搅拌器) 中匀化,
c) 在搅拌式球磨机中研磨,
d) 任选加入有机粘合剂,
e) 喷雾干燥,
f) 用水和任选另外的助压剂润湿颗粒物,
g) 轴向压制块料,
h) 切削加工坯料状态或预烧结状态的块料,
i) 烧结,
j) 硬质加工。
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CN113929452A (zh) * | 2020-06-29 | 2022-01-14 | 比亚迪股份有限公司 | 氧化锆复合陶瓷及其制备方法、壳体组件和电子设备 |
CN113929452B (zh) * | 2020-06-29 | 2022-10-18 | 比亚迪股份有限公司 | 氧化锆复合陶瓷及其制备方法、壳体组件和电子设备 |
CN115304370A (zh) * | 2021-05-07 | 2022-11-08 | 苏州宸泰医疗器械有限公司 | 氧化锆-钇铝石榴石复合陶瓷及由其制备的骨植入假体 |
CN113321505A (zh) * | 2021-08-03 | 2021-08-31 | 中南大学湘雅医院 | 一种氧化锆基陶瓷材料及其制备方法 |
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BR112015003594A2 (pt) | 2017-07-04 |
BR112015003594B1 (pt) | 2021-09-28 |
DE102013216440A1 (de) | 2014-02-20 |
RU2015109629A (ru) | 2016-10-10 |
CN104736498A (zh) | 2015-06-24 |
US9783459B2 (en) | 2017-10-10 |
RU2640853C2 (ru) | 2018-01-12 |
JP6333254B2 (ja) | 2018-05-30 |
EP2885259A1 (de) | 2015-06-24 |
WO2014029757A1 (de) | 2014-02-27 |
EP2885259B1 (de) | 2020-10-07 |
US20150175485A1 (en) | 2015-06-25 |
JP2015533754A (ja) | 2015-11-26 |
CN104736498B (zh) | 2018-11-13 |
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