US20240026296A1 - Lithium disilicate glass-ceramic compositions and methods thereof - Google Patents
Lithium disilicate glass-ceramic compositions and methods thereof Download PDFInfo
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- US20240026296A1 US20240026296A1 US18/376,260 US202318376260A US2024026296A1 US 20240026296 A1 US20240026296 A1 US 20240026296A1 US 202318376260 A US202318376260 A US 202318376260A US 2024026296 A1 US2024026296 A1 US 2024026296A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 33
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000006136 disilicate glass ceramic Substances 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000006112 glass ceramic composition Substances 0.000 claims abstract description 58
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 21
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 19
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 15
- 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 claims abstract description 15
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 15
- 239000010456 wollastonite Substances 0.000 claims abstract description 15
- 229910000500 β-quartz Inorganic materials 0.000 claims abstract description 14
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000002241 glass-ceramic Substances 0.000 claims description 54
- 239000006064 precursor glass Substances 0.000 claims description 32
- 238000003279 ceramming Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000000975 bioactive effect Effects 0.000 description 31
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- 239000011521 glass Substances 0.000 description 24
- 108020004414 DNA Proteins 0.000 description 15
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- 229910052587 fluorapatite Inorganic materials 0.000 description 10
- 102000053602 DNA Human genes 0.000 description 9
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- 239000013078 crystal Substances 0.000 description 7
- KPKZJLCSROULON-QKGLWVMZSA-N Phalloidin Chemical compound N1C(=O)[C@@H]([C@@H](O)C)NC(=O)[C@H](C)NC(=O)[C@H](C[C@@](C)(O)CO)NC(=O)[C@H](C2)NC(=O)[C@H](C)NC(=O)[C@@H]3C[C@H](O)CN3C(=O)[C@@H]1CSC1=C2C2=CC=CC=C2N1 KPKZJLCSROULON-QKGLWVMZSA-N 0.000 description 6
- ZYFVNVRFVHJEIU-UHFFFAOYSA-N PicoGreen Chemical compound CN(C)CCCN(CCCN(C)C)C1=CC(=CC2=[N+](C3=CC=CC=C3S2)C)C2=CC=CC=C2N1C1=CC=CC=C1 ZYFVNVRFVHJEIU-UHFFFAOYSA-N 0.000 description 6
- 210000000963 osteoblast Anatomy 0.000 description 6
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
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- 239000002609 medium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000012890 simulated body fluid Substances 0.000 description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 3
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 3
- 239000012109 Alexa Fluor 568 Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 108010009711 Phalloidine Proteins 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000005313 bioactive glass Substances 0.000 description 3
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 3
- 229910052912 lithium silicate Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical group [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003462 bioceramic Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 210000002510 keratinocyte Anatomy 0.000 description 2
- 239000003103 lithium disilicate glass Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- 238000010899 nucleation Methods 0.000 description 2
- 230000001582 osteoblastic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
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- DAEPDZWVDSPTHF-UHFFFAOYSA-M sodium pyruvate Chemical compound [Na+].CC(=O)C([O-])=O DAEPDZWVDSPTHF-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101000577121 Homo sapiens Monocarboxylate transporter 3 Proteins 0.000 description 1
- 101000577126 Homo sapiens Monocarboxylate transporter 4 Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 102100025275 Monocarboxylate transporter 3 Human genes 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007984 Tris EDTA buffer Substances 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
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- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000010478 bone regeneration Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001054 cortical effect Effects 0.000 description 1
- 210000004748 cultured cell Anatomy 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 229910001409 divalent cation oxide Inorganic materials 0.000 description 1
- 210000000959 ear middle Anatomy 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
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- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000009610 hypersensitivity Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 239000002667 nucleating agent Substances 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 230000002298 osteoproductive effect Effects 0.000 description 1
- 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 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940054269 sodium pyruvate Drugs 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007668 thin rolling process Methods 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
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 210000003606 umbilical vein Anatomy 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N5/00—Undifferentiated human, animal or plant cells, e.g. cell lines; Tissues; Cultivation or maintenance thereof; Culture media therefor
- C12N5/06—Animal cells or tissues; Human cells or tissues
- C12N5/0602—Vertebrate cells
- C12N5/0652—Cells of skeletal and connective tissues; Mesenchyme
- C12N5/0654—Osteocytes, Osteoblasts, Odontocytes; Bones, Teeth
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K35/00—Medicinal preparations containing materials or reaction products thereof with undetermined constitution
- A61K35/12—Materials from mammals; Compositions comprising non-specified tissues or cells; Compositions comprising non-embryonic stem cells; Genetically modified cells
- A61K35/32—Bones; Osteocytes; Osteoblasts; Tendons; Tenocytes; Teeth; Odontoblasts; Cartilage; Chondrocytes; Synovial membrane
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/111—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0014—Biodegradable glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
- C03C2205/06—Compositions applicable for the manufacture of vitreous enamels or glazes for dental use
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/20—Glass-ceramics matrix
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N2500/00—Specific components of cell culture medium
- C12N2500/05—Inorganic components
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N2533/00—Supports or coatings for cell culture, characterised by material
- C12N2533/10—Mineral substrates
- C12N2533/12—Glass
Definitions
- the disclosure relates to glass-ceramic compositions, bioactive glass-ceramic compositions and articles made from the glass-ceramic compositions, and to methods of making and using the bioactive glass-ceramic compositions and articles.
- the disclosure provides a group of glass-ceramic compositions each having lithium disilicate as a first major crystal phase, and at least one of wollastonite, fluoroapatite, cristobalite, ⁇ -quartz, lithiophosphate, or a mixture thereof, as a second minor phase.
- the disclosed compositions can comprise a source of, for example, 50 to 75 wt % SiO 2 , 1 to 5 wt % Al 2 O 3 , 1 to 8 wt % P 2 O 5 , 2 to 10 wt % CaO, 5 to 20 wt % Li 2 O, 0.5 to 5 wt % Na 2 O, 0.5 to 8 wt % ZrO 2 , and 0.1 to 1.0 F ⁇ wt % (i.e., fluoride ion), based on a 100 wt % total of the composition.
- a source of for example, 50 to 75 wt % SiO 2 , 1 to 5 wt % Al 2 O 3 , 1 to 8 wt % P 2 O 5 , 2 to 10 wt % CaO, 5 to 20 wt % Li 2 O, 0.5 to 5 wt % Na 2 O, 0.5 to 8 wt % ZrO 2 , and 0.1 to
- the disclosed compositions can further comprise a source of, for example, 0.1 to 10 wt % B 2 O 3 , based on a 100 wt % total of the composition.
- the disclosure provides a glass-ceramic composition or glass-ceramic articles made from the composition, having a combination of high strength and high toughness.
- the disclosure provides a glass-ceramic composition having excellent biocompatibility.
- the disclosure provides methods of making and using the disclosed compositions.
- FIG. 1 shows X-ray diffraction spectra of example compositions 7 to 10. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr.
- FIGS. 2 A to 2 D show SEM images of polished surfaces in example compositions 7 to 10 corresponding to FIGS. 2 A, 2 B, 2 C, and 2 D , respectively.
- FIGS. 3 A to 3 D show confocal SEM images of MC3T3 cell growth in disclosed compositions 7 to 10 corresponding to FIGS. 3 A, 3 B, 3 C, and 3 D , respectively.
- FIGS. 4 A and 4 B show Day 1 attachment and proliferation of MC3T3 cells on disclosed bioactive glass-ceramic discs: absolute level (absolute cell number; 4 A) and relative levels with respect to an in vitro control: a Tissue Culture Treated® (TCT) well (relative cell number; 4 B).
- absolute level absolute cell number
- TCT Tissue Culture Treated®
- FIGS. 5 A and 5 B show cell proliferation results for disclosed compositions 7 to 10.
- the disclosed method of making and using provide one or more advantageous features or aspects, including for example as discussed below.
- Features or aspects recited in any of the claims are generally applicable to all facets of the invention. Any recited single or multiple feature or aspect in any one claim can be combined or permuted with any other recited feature or aspect in any other claim or claims.
- Glass Glass, “glasses,” or like terms can refer to a glass or a glass-ceramic.
- Glass article can refer to any object made wholly or partly of any of the disclosed glass or glass-ceramic compositions.
- Bioactivity Index index of bioactivity
- I B index of bioactivity
- osteoproductive Class A having both intracellular and extracellular responses, e.g., 45S5 Bioglass®
- osteoconductive Class B extracellular response only at interface, e.g., synthetic hydroxyapatite
- the term “about” also encompasses amounts that differ due to aging of a composition or formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a composition or formulation with a particular initial concentration or mixture.
- indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
- compositions and methods of the disclosure can include any value or any combination of the values, specific values, more specific values, and preferred values described herein, including explicit or implicit intermediate values and ranges.
- Bioactive materials having high strength and toughness are in significant demand, for example, for the regeneration of bone and teeth.
- Glass-ceramics based on lithium disilicate offer highly desirable mechanical properties, including high body strength and fracture toughness, due to their microstructures of randomly-oriented interlocking crystals.
- Glass-ceramics having fracture toughness values of 2 to 3 MPa ⁇ m 1/2 are achievable in the system of glass-ceramics based on lithium disilicate compositions (see commonly owned and assigned U.S. Ser. No. 61/874,870).
- Lithium disilicate glass-ceramics have been widely used in the fabrication of single and multiple dental restorations. However, these glass-ceramics have not been used in bone repair due to their relatively low bioactivity.
- bioceramics based on apatite and wollastonite have demonstrated high bioactivity but do not have sufficient mechanical strength compared to, for example, cortical bone (Hench, L. L., Bioceramics, J Am Ceram Soc, 1998, 81: 1705-1728).
- the disclosure provides a group of glass-ceramic compositions having a phase assemblage containing a major phase of lithium disilicate and a minor phase or phases of, for example, apatite or wollastonite.
- These superior compositions exhibit an excellent combination of high mechanical strength and high bioactivity, which makes them excellent for hard tissue regeneration.
- WO 2015200017 ('017), entitled “Process for producing a sintered lithium disilicate glass ceramic dental restoration and kit of parts,” mentions a process for producing a sintered lithium disilicate glass ceramic dental restoration out of a porous 3-dim article.
- the presently disclosed compositions have a different phase assemblage, for example, the disclosed compositions have lithium disilicate and apatite, whereas '017 has only lithium disilicate, and the presently disclosed compositions are bioactive but not the '017 compositions. Additionally, the presently disclosed compositions have CaO and F to produce the apatite phase.
- U.S. Pat. No. 7,166,548 mentions an apatite glass ceramic, which contains at least one glass phase and at least one apatite phase and is characterized in that at least one of the apatite phases is a phosphate-free and fluorine-free siliceous oxyapatite phase.
- these materials exclude phosphate and fluorine, which is present in the presently disclosed compositions.
- the disclosure provides a glass-ceramic composition, comprising:
- the disclosure provides a glass-ceramic composition wherein the first crystalline phase and the second crystalline phase, in combination, comprise a source of:
- the glass-ceramic composition can further comprise a source of 0.1 to 10 wt % B 2 O 3 , based on a 100 wt % total of the composition.
- the first crystalline phase and the second crystalline phase in combination, can comprise a source of:
- the abovementioned composition can be a preferred or a most preferred composition and can comprise, consist of, or consist essentially of, the abovementioned composition components.
- the disclosed bioactive compositions and articles can be a preferred or most preferred composition or article and can comprise, consist of, or consist essentially of, the disclosed bioactive composition or article.
- the disclosed methods of making and methods of using can be a preferred or most preferred method and can comprise, consist of, or consist essentially of, the disclosed methods.
- the composition can have a high strength of from 200 MPa to 500 MPa, for example, from at least 200 MPa, at least 300 MPa, or at least 400 MPa, including intermediate values and ranges.
- the composition can have a high fracture toughness of from 1.4 to 2.0 MPa ⁇ m 1/2 , for example, from at least 1.4, 1.6, 1.8, or 2.0 MPa ⁇ m 1/2 , including intermediate values and ranges.
- the composition can have a combination of high strength of from 200 MPa to 500 MPa, and high fracture toughness of from 1.4 to 2.0 MPa ⁇ m 1/2 .
- the composition can be prepared from a precursor glass composition comprising a source of, for example:
- the abovementioned precursor glass composition does not change significantly upon ceramming.
- the disclosure provides a method of making the abovementioned glass-ceramic compositions comprising, for example:
- the method of making can further comprise, for example, ion exchanging the resulting glass-ceramic composition to create at least one compressive stress layer on at least one surface of the article to increase mechanical strength of the article.
- the disclosure provides a bioactive composition, comprising:
- the glass-ceramic composition can comprise, for example, a source of:
- the glass-ceramic composition can comprise, for example, a source of:
- the abovementioned bioactive composition can further comprise, for example, a source of 0.1 to 10 wt % B 2 O 3 , based on a 100 wt % total of the composition.
- the disclosure provides a method of culturing osteoblast cells, i.e., a method of using the disclosed bioactive composition, comprising, for example:
- the glass-ceramic composition of the bioactive composition can be combined or contacted with the suitable liquid medium prior to being contacted with the live osteoblast cell(s).
- the contacting produces a proliferation of the osteoblast cells on the surface of the bioactive composition.
- the contacting produces a proliferation of the osteoblast cells in the suitable liquid medium, such as the culture medium of MC3T3 cells: i.e., alpha-MEM supplemented with 10% fetal bovine serum and 1 mM sodium pyruvate.
- suitable liquid medium such as the culture medium of MC3T3 cells: i.e., alpha-MEM supplemented with 10% fetal bovine serum and 1 mM sodium pyruvate.
- the suitable liquid medium can include, for example, a simulated body fluid (SBF) composition.
- SBF is used for testing apatite formation activity of bioactive glasses/glass-ceramics.
- the disclosed bioactive glass-ceramics form in-situ a biologically active apatite layer (e.g., the mineral phase of bone and teeth) that can bond to bone and teeth, and can even bond to soft tissue.
- a biologically active apatite layer e.g., the mineral phase of bone and teeth
- the potential applications of the disclosed bioactive glass-ceramics can include, for example, monolithic articles, composites, films, coating, or like forms, for use in repair of load-bearing bones, dental regeneration, treatment of dental hypersensitivity, artificial vertebrae, spinous spacers, intervertebral spacers, iliac spacers, granular fillers, scaffolds, middle-ear implant and in other types of small-bone replacement, wound healing, and like applications.
- the disclosed bioactive glass-ceramics are biocompatible with, for example, osteoblasts, keratinocytes, human umbilical vein endothelial cells (HUVEC), etc. (see for example, T. Kokubo et al., “How useful is SBF in predicting in vivo bone bioactivity?”, Biomaterials, 27[15] 2907-15 (2006)).
- the disclosed compositions and disclosed bioactive compositions can also have application in, for example: angiogenesis (HUVEC cells), wound healing (keratinocytes), bone tissue engineering (MC3T3 cells), and like applications.
- angiogenesis HUVEC cells
- wound healing keratinocytes
- M3T3 cells bone tissue engineering
- the disclosed composition is biocompatible with various cell types in various applications, and are biologically active (i.e., bioactive).
- compositions and methods thereof are advantaged in several aspects, including for example:
- the disclosed bioactive glass-ceramic compositions can further comprise, for example, a form factor selected from a hollow microsphere, a solid microsphere, or a combination thereof, that is, where the glass composition has a particle shape, such as a sphere, an elongated sphere or egg-shape, a rod, or like geometries.
- Table 1 lists representative examples of the disclosed compositions. The ceramming cycle for all examples 1 to 15 was 700° C. for 2 hr and 800° C. for 4 hr.
- A Lithium disilicate, cristobalite, wollastonite, ß-quartz, lithiophosphate.
- B Lithium disilicate, wollastonite, lithiophosphate.
- C Lithium disilicate, lithium metasilicate, wollastonite, lithiophospahte.
- D Lithium disilicate, ß-quartz, lithiophospahte.
- E Lithium disilicate, cristobalite, fluoroapatite, ß-quartz.
- F Lithium disilicate, fluoroapatite, ß-quartz, lithiophosphate.
- G Lithium disilicate, fluoroapatite, lithium metasilicate, ß-quartz.
- H Lithium disilicate, fluoroapatite, ß-quartz.
- the disclosed compositions can be free of (e.g., zero ppm or ppb), or substantially free of (e.g., trace amounts less than several ppm or ppb), at least one of, for example, K 2 O, K 2 CO 3 , Ca 3 (PO 4 ) 2 , MgO, TiO 2 , As 2 O 3 , Sb 2 O 3 , or combinations or mixtures thereof.
- the disclosure provides precursor glass compositions that can be cerammed to produce glass-ceramics having excellent mechanical properties and biocompatibility.
- the disclosure provides glass-ceramics having high mechanical strength by forming an interlocking structure in the cerammed articles, which forces cracks to propagate along a tortuous path. Additionally, the presence of minor crystallite phases such as fluoroapatite and wollastonite in the disclosed compositions is beneficial to the growth, proliferation, and function of osteoblastic cell lines.
- the precursor glass or source glass can comprise, for example, 50 to 75 wt % SiO 2 , 1 to 5 wt % Al 2 O 3 , 5 to 20 wt % Li 2 O, 0.5 to 5 wt % Na 2 O, 0.5 to 8 wt % ZrO 2 , and 0.1 to 1.0 F ⁇ wt % (i.e., fluoride ion), based on a 100 wt % total of the composition.
- F ⁇ wt % i.e., fluoride ion
- a more preferred precursor glass composition can be, for example, 50 to 60 wt % SiO 2 , 1.0 to 3.0 wt % Al 2 O 3 , 0.1 to 4.0 wt % B 2 O 3 , 7.5 to 12.5 wt % Li 2 O, 0.5 to 2.0 wt % Na 2 O, 1.0 to 4.0 wt % ZrO 2 , and 0.2 to 0.8 wt % F ⁇ ion based on a 100 weight percentage total (see Table 1).
- the precursor glasses can be cerammed into glass-ceramic articles having high crystallinity of, for example, 80% or more, such as 80 to 95%.
- the major crystallite phases are comprised of lithium disilicate.
- the minor crystallite phases can be comprised of, for example, fluoroapatite, wollastonite, cristobalite, ⁇ -quartz, lithiophosphate, or mixtures thereof depending on composition targeted.
- FIG. 1 shows X-ray diffraction spectra of example compositions 7 to 10, where the reference numerals 7 , 8 , 9 , and 10 , correspond to example compositions 7 to 10, respectively, in Table 1.
- the significant peaks are identified (with marker shapes) as: lithium disilicate (asterisk), lithium metasilicate (triangle), fluoroapatite (dot), beta-quartz (square), and cristobalite (diamond). All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr.
- the disclosed glass-ceramic articles composed of interlocking lithium disilicate can be easily obtained by ceramming precursor glasses at temperatures of from 700 to 900° C. for a period of time.
- a grain size of the lithium disilicate phase can be larger than 1 micrometer having a high aspect ratio that is typically formed in glass-ceramics.
- FIGS. 2 A to 2 D show SEM images of polished surfaces in example compositions 7 to 10 corresponding to FIGS. 2 A, 2 B, 2 C, and 2 D , respectively. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. Specimens were etched in 1% HF for one min prior to observation.
- interlocking crystals can be a significant factor in developing toughening mechanisms including, for example, crack deflection and tortuous crack path, which mechanisms can contribute to the observed high fracture toughness and high flexural strength (Table 1).
- a fracture toughness of over 1.5 MPa ⁇ m 1/2 and a flexural strength of over 300 MPa can be achieved in selected glass-ceramic compositions.
- the disclosed glass-ceramic product or residual glass can be ion exchanged to create a compressive stress layer in the surface of a ware to further improve mechanical strength.
- FIGS. 3 A to 3 D show confocal SEM images of MC3T3 cell growth in the disclosed compositions 7 to 10 corresponding to FIGS. 3 A, 3 B, 3 C, and 3 D , respectively. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. Cells were cultured one day, fixed with 4% formaldehyde, and then stained with Alexa Fluor 568 phalloidin and DAPI prior to the confocal imaging.
- the disclosed glass-ceramics can be manufactured using a thin rolling, a float, a casting process, and like methods; and scaffolds can be produced using, for example, rapid prototyping, polymer foam replication, particle sintering, and like methods. Glass-ceramics of desired forms can be used to support cell growth and hard tissue regeneration.
- the realized mechanical strength, biocompatibility, and biodegradation of the disclosed compositions can be influenced by the glass compositions.
- the disclosed glass compositions can further include, for example: SiO 2 which serves as the primary glass-forming oxide for precursor glass and can function to stabilize the networking structure of glass and glass-ceramics.
- the concentration of SiO 2 should be sufficiently high to form a lithium disilicate crystal phase when the precursor glass is heat treated to convert to a glass-ceramic (i.e., cerammed).
- the glasses can't contain too much SiO 2 since the melting temperature (200 poise temperature) of pure SiO 2 or high-SiO 2 glasses is undesirably high.
- glass or glass-ceramic compositions can comprise, for example, 68 to 82 wt % SiO 2 , based on a 100 wt % total weight.
- the Al 2 O 3 may also provide stabilization to the networking structure.
- Al 2 O 3 is favorable to the improvement of mechanical properties and chemical durability. However, too much Al 2 O 3 generally increases the viscosity of the melt and decreases the fraction of lithium disilicate crystals to an extent that no interlocking structure can be formed.
- the Al 2 O 3 concentration is preferably maintained in a reasonable range of, for example, from 1 to 5 wt %.
- the addition of B 2 O 3 can be beneficial to improved crack-resistance of the glass-ceramics, which is helpful for dental applications.
- a higher boron concentration can increase the degradation rate of the bioactive compositions, which property may be desired in applications such as bone regeneration.
- Li 2 O is another significant component in the disclosed precursor glass compositions.
- Li 2 O is advantageous for forming lithium disilicate crystal phases.
- Li 2 O is called for to have at least 8 wt % Li 2 O to obtain glass-ceramics having lithium disilicate as a predominant phase.
- the Li 2 O content gets too high, such as greater than 15 wt %, the precursor glasses become very fluid with low resistivity making it difficult to melt or form.
- the disclosed glass and glass-ceramic compositions can include, for example, from 2 to 6 wt % P 2 O 5 , for example, as a nucleating agent to produce bulk nucleation. If the P 2 O 5 concentration is too low, such as less than 2 wt %, the precursor glass does not crystallize. If the P 2 O 5 concentration is too high, such as greater than 6 wt %, the devitrification upon cooling during precursor glass forming, can be difficult to control.
- divalent cation oxides such as alkaline earth oxides
- divalent cation oxides can also be used to improve the melting behavior and the bioactivity of the glass.
- CaO was found to combine with P 2 O 5 to form apatite, or with SiO 2 to form wollastonite. Both apatite and wollastonite are known bioactive ceramics (see Hench, L. L., supra.).
- including Na 2 O in the precursor glass in an amount of from 0.1 to 5 wt % can reduce the melting temperature of the precursor glass, and can shorten the ceramming cycle. Furthermore, including Na 2 O in the precursor glass can also increase the thermal expansion after ceramming if a higher thermal expansion (i.e., CTE) is desired in the glass-ceramic articles.
- CTE thermal expansion
- melting was accomplished at an elevated temperature, such as above 1300° C., to fuse the precursor glass materials.
- ceramming was the heat treatment of the melted glass that was used to crystallize the glass into a glass-ceramic material.
- the precursor glass source materials Prior to melting, the precursor glass source materials were vigorously mixed in a plastic jar using a Turbula® mixer. Then the mixtures were transferred to a platinum crucible with an internal volume of approximately 650 cc and heated at 700° C. for 2 hr then 800° C. for 4 hr, and then the glass melt was poured on a steel plate, and annealed at 500° C.
- Glass-ceramic discs were prepared from cerammed parts. Precursor glass patties were cerammed in an electronic furnace using a cycle of 700° C. to 2 hr for nucleation and then 800° C. for 4 hr for crystal growth. After ceramming, the discs (12.5 mm in diameter ⁇ 2.0 mm thick) were core-drilled using a diamond drill, and then ground and polished to a 1.0 micrometer finish using a CeO 2 slurry. All finished discs were cleaned by sonicating in an ultrasonic sonicator for 10 min.
- Example 2 Glass-ceramic discs of Example 2 (made from compositions of the above working Example 1) were placed in wells of 24 well tissue culture treated microplates. Each composition has duplicate discs. MC 3T3 cells were then seeded (20K/2 mL) into the wells and some wells without any discs (Tissue Culture Treated (TCT) control). The microplates were cultured for 1, 4, or 7 days. Cells in the 1 day culture microplate were fixed with 4% formaldehyde, and then stained with Alexa Fluor 568 phalloidin and DAPI prior to the confocal imaging.
- FIGS. 4 A and 4 B show Day 1 attachment and proliferation of MC3T3 cells on disclosed bioactive glass-ceramic discs of Example compositions 7, 8, 9, and 19 (see Table 1) with respect to a reference bioactive glass control compositions 1 (C-1) and an in vitro control: a Tissue Culture Treated® (TCT) well: absolute level (absolute cell number; 4 A) and relative levels (relative cell number; 4 B).
- TCT Tissue Culture Treated®
- FIGS. 5 A and 5 B show cell proliferation results for disclosed compositions 7 to 10.
- Cells in the day 4 (D4) and day 7 (D7) culture plates were digested with the digestion buffer (125 microg/mL papain, 2 mM L-cysteine, 2 mM EDTA) at 65° C. for 16 hrs, the dsDNA amount was measured using Quant-iTTM PicoGreen® dsDNA Kit (Thermo Fisher). The increase of DNA concentration with increasing culture time provides additional evidence of their excellent biocompatibility.
- the digestion buffer 125 microg/mL papain, 2 mM L-cysteine, 2 mM EDTA
- MC3T3 cells were digested with papain and the amount of DNA was measured using a PicoGreen assay.
- D4 or D7 refers to Day 4 or Day 7 (as in “the 4 th day or 7 th day of cell culture”).
- TCT refers to a tissue culture treated microplate substrate available from Corning, Inc®. Glass-ceramic discs were placed in wells of 24 well tissue culture treated microplates. Each composition has duplicate discs.
- MC 3T3 cells were then seeded (20K/2 mL) into the wells and some wells without any discs (TCT control). The microplates were cultured for 4 or 7 days.
- cells were digested with a digestion buffer (D-PBS containing 125 microg/mL papain, 2 mM L-cysteine, 2 mMM EDTA) at 65° C. in humid environment with shaking (60 rpm) for 16 hrs.
- a digestion buffer D-PBS containing 125 microg/mL papain, 2 mM L-cysteine, 2 mMM EDTA
- the collected digestion solution was briefly centrifuged to remove any remaining particles.
- the dsDNA amount in the supernatant was measured using Quant-iTTM PicoGreen® dsDNA Kit (Thermo Fisher) according to the manufacturer's instruction.
- MC3T3E1 Subclone 14 (ATCC® CRL2594TM)(see atcc.org/products/all/CRL-2594.aspx).
- Quant-iTTM PicoGreen® dsDNA Kit (Invitrogen, #P11496). This kit contains Quant-iTTM PicoGreen® dsDNA Reagent (10 vials, each containing 100 microL aliquots), 25 mL of 20 ⁇ TE buffer, 1 mL of 100 microg/mL Lambda DNA (dsDNA standard), Papain (Sigma-Aldrich, #P4762-25MG), L-cysteine (Sigma-Aldrich, #C1276-10G), EDTA (Sigma-Aldrich, #E6511), D-PBS (Thermo Fisher, #14190), a shaker set to 65° C., and a plate reader.
- Quant-iTTM PicoGreen® dsDNA Reagent 10 vials, each containing 100 microL aliquots), 25 mL of 20 ⁇ TE buffer, 1 mL of 100 microg/mL Lambda DNA (dsDNA standard), Papain (Sigma-Ald
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Abstract
A glass-ceramic composition as defined herein. The glass-ceramic composition includes a first crystalline phase comprising lithium disilicate. The glass-ceramic composition can include up to 10 wt % CaO, up to 5 wt % Na2O, up to 10 wt % B2O3, and greater than 0.5 wt % ZrO2. The glass-ceramic composition can also include from 50 to 75 wt % SiO2, from 1 to 5 wt % Al2O3, from 1 to 8 wt % P2O5, and from 5 to 20 wt % Li2O. In aspects, the glass-ceramic composition can include a second crystalline phase including wollastonite, apatite, cristobalite, β-quartz, lithiophosphate, or a combination thereof. Also disclosed are methods of making and using the disclosed compositions.
Description
- This application is a continuation of and claims the benefit of priority under 35 U.S.C. § 120 of U.S. patent application Ser. No. 16/163,013 filed on Oct. 17, 2018, which is a divisional of and claims the benefit of priority under 35 U.S.C. § 121 of U.S. patent application Ser. No. 15/603,006, filed May 23, 2017, which claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Patent Application No. 62/342,381 filed May 27, 2016, the contents of both of which are relied upon and incorporated herein by reference in their entirety.
- The present application is related commonly owned and assigned USSN Provisional Application Nos., filed concurrently herewith:
-
- 62/342,384, entitled “BIOACTIVE ALUMINOBORATE GLASSES”;
- 62/342,377, entitled “MAGNETIZABLE GLASS CERAMIC COMPOSITION AND METHODS THEREOF”;
- 62/342,391, entitled “BIODEGRADABLE MICROBEADS”;
- 62/342,411, entitled “BIOACTIVE GLASS MICROSPHERES”; and
- 62/342,426, entitled “BIOACTIVE BOROPHOSPHATE GLASSES”; but does not claim priority thereto.
- The present application is also related to commonly owned and assigned U.S. Application Ser. No. 62/189,880, filed Jul. 7, 2015, entitled “ANTIMICROBIAL PHASE-SEPARATING GLASS AND GLASS CERAMIC ARTICLES AND LAMINATES,” which mentions a copper containing laminate having a degradable phase, which phase liberates cooper ion, and a non-degradable phase; and 61/874,870, filed Sep. 6, 2013, entitled “High strength glass-ceramics having lithium disilicate and beta-spodumene structures,” but does not claim priority thereto.
- The entire disclosure of each publication or patent document mentioned herein is incorporated by reference.
- The disclosure relates to glass-ceramic compositions, bioactive glass-ceramic compositions and articles made from the glass-ceramic compositions, and to methods of making and using the bioactive glass-ceramic compositions and articles.
- In embodiments, the disclosure provides a group of glass-ceramic compositions each having lithium disilicate as a first major crystal phase, and at least one of wollastonite, fluoroapatite, cristobalite, β-quartz, lithiophosphate, or a mixture thereof, as a second minor phase.
- In embodiments, the disclosed compositions can comprise a source of, for example, 50 to 75 wt % SiO2, 1 to 5 wt % Al2O3, 1 to 8 wt % P2O5, 2 to 10 wt % CaO, 5 to 20 wt % Li2O, 0.5 to 5 wt % Na2O, 0.5 to 8 wt % ZrO2, and 0.1 to 1.0 F− wt % (i.e., fluoride ion), based on a 100 wt % total of the composition.
- In embodiments, the disclosed compositions can further comprise a source of, for example, 0.1 to 10 wt % B2O3, based on a 100 wt % total of the composition.
- In embodiments, the disclosure provides a glass-ceramic composition or glass-ceramic articles made from the composition, having a combination of high strength and high toughness.
- In embodiments, the disclosure provides a glass-ceramic composition having excellent biocompatibility.
- In embodiments, the disclosure provides methods of making and using the disclosed compositions.
- In embodiments of the disclosure:
-
FIG. 1 shows X-ray diffraction spectra ofexample compositions 7 to 10. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. -
FIGS. 2A to 2D show SEM images of polished surfaces inexample compositions 7 to 10 corresponding toFIGS. 2A, 2B, 2C, and 2D , respectively. -
FIGS. 3A to 3D show confocal SEM images of MC3T3 cell growth in disclosedcompositions 7 to 10 corresponding toFIGS. 3A, 3B, 3C, and 3D , respectively. -
FIGS. 4A and 4B showDay 1 attachment and proliferation of MC3T3 cells on disclosed bioactive glass-ceramic discs: absolute level (absolute cell number; 4A) and relative levels with respect to an in vitro control: a Tissue Culture Treated® (TCT) well (relative cell number; 4B). -
FIGS. 5A and 5B show cell proliferation results for disclosedcompositions 7 to 10. - Various embodiments of the disclosure will be described in detail with reference to drawings, if any. Reference to various embodiments does not limit the scope of the invention, which is limited only by the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not limiting and merely set forth some of the many possible embodiments of the claimed invention.
- In embodiments, the disclosed method of making and using provide one or more advantageous features or aspects, including for example as discussed below. Features or aspects recited in any of the claims are generally applicable to all facets of the invention. Any recited single or multiple feature or aspect in any one claim can be combined or permuted with any other recited feature or aspect in any other claim or claims.
- “Glass,” “glasses,” or like terms can refer to a glass or a glass-ceramic.
- “Glass article,” or like terms can refer to any object made wholly or partly of any of the disclosed glass or glass-ceramic compositions.
- “Bioactivity Index” “index of bioactivity,” “IB,” or like terms or symbols refer to, for example, the time for more than 50% of the interface of a specific bioactive material to be bonded by a biological material such as bone, tissue, and like materials. Mathematically, a bioactivity index (according to Hench; see Cao, W., et al., Bioactive Materials, Ceramics International, 22 (1996) 493-507) is, IB=100/t0.5bb, where t0.5bb is the time for more than 50% of a bioactive material's interface, such as an implant, to be bonded by a biological material such as bone, tissue, and like materials, including osteoproductive (Class A having both intracellular and extracellular responses, e.g., 45S5 Bioglass®) and osteoconductive (Class B extracellular response only at interface, e.g., synthetic hydroxyapatite) materials.
- “Include,” “includes,” or like terms means encompassing but not limited to, that is, inclusive and not exclusive.
- “About” modifying, for example, the quantity of an ingredient in a composition, concentrations, volumes, process temperature, process time, yields, flow rates, pressures, viscosities, and like values, and ranges thereof, or a dimension of a component, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example: through typical measuring and handling procedures used for preparing materials, compositions, composites, concentrates, component parts, articles of manufacture, or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods; and like considerations. The term “about” also encompasses amounts that differ due to aging of a composition or formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a composition or formulation with a particular initial concentration or mixture.
- “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
- The indefinite article “a” or “an” and its corresponding definite article “the” as used herein means at least one, or one or more, unless specified otherwise.
- Abbreviations, which are well known to one of ordinary skill in the art, may be used (e.g., “h” or “hrs” for hour or hours, “g” or “gm” for gram(s), “mL” for milliliters, “rt” for room temperature, “nm” for nanometers, and like abbreviations).
- Specific and preferred values disclosed for components, ingredients, additives, dimensions, conditions, times, and like aspects, and ranges thereof, are for illustration only; they do not exclude other defined values or other values within defined ranges. The composition and methods of the disclosure can include any value or any combination of the values, specific values, more specific values, and preferred values described herein, including explicit or implicit intermediate values and ranges.
- Bioactive materials having high strength and toughness are in significant demand, for example, for the regeneration of bone and teeth. Glass-ceramics based on lithium disilicate offer highly desirable mechanical properties, including high body strength and fracture toughness, due to their microstructures of randomly-oriented interlocking crystals. Glass-ceramics having fracture toughness values of 2 to 3 MPa·m1/2 are achievable in the system of glass-ceramics based on lithium disilicate compositions (see commonly owned and assigned U.S. Ser. No. 61/874,870). Lithium disilicate glass-ceramics have been widely used in the fabrication of single and multiple dental restorations. However, these glass-ceramics have not been used in bone repair due to their relatively low bioactivity. In contrast, bioceramics based on apatite and wollastonite have demonstrated high bioactivity but do not have sufficient mechanical strength compared to, for example, cortical bone (Hench, L. L., Bioceramics, J Am Ceram Soc, 1998, 81: 1705-1728).
- In embodiments, the disclosure provides a group of glass-ceramic compositions having a phase assemblage containing a major phase of lithium disilicate and a minor phase or phases of, for example, apatite or wollastonite. These superior compositions exhibit an excellent combination of high mechanical strength and high bioactivity, which makes them excellent for hard tissue regeneration.
- WO 2015200017 ('017), entitled “Process for producing a sintered lithium disilicate glass ceramic dental restoration and kit of parts,” mentions a process for producing a sintered lithium disilicate glass ceramic dental restoration out of a porous 3-dim article. In contrast, the presently disclosed compositions have a different phase assemblage, for example, the disclosed compositions have lithium disilicate and apatite, whereas '017 has only lithium disilicate, and the presently disclosed compositions are bioactive but not the '017 compositions. Additionally, the presently disclosed compositions have CaO and F to produce the apatite phase.
- US 20150087493 mentions lithium disilicate apatite glass-ceramics, which are characterized by a high chemical stability and can be used as restoration material in dentistry. However, these materials all include K2O, which is absent from the presently disclosed compositions.
- U.S. Pat. No. 7,166,548 mentions an apatite glass ceramic, which contains at least one glass phase and at least one apatite phase and is characterized in that at least one of the apatite phases is a phosphate-free and fluorine-free siliceous oxyapatite phase. However, these materials exclude phosphate and fluorine, which is present in the presently disclosed compositions.
- In embodiments, the disclosure provides a glass-ceramic composition, comprising:
-
- a first crystalline phase comprised of lithium disilicate; and
- a second crystalline phase selected from the group consisting of at least one of: wollastonite, fluoroapatite, cristobalite, β-quartz, lithiophosphate, or a combination thereof.
- In embodiments, the disclosure provides a glass-ceramic composition wherein the first crystalline phase and the second crystalline phase, in combination, comprise a source of:
-
- 50 to 75 wt % SiO2,
- 1 to 5 wt % Al2O3,
- 1 to 8 wt % P2O3,
- 2 to 10 wt % CaO,
- 5 to 20 wt % Li2O,
- 0.5 to 5 wt % Na2O,
- 0.5 to 8 wt/ZrO2, and
- 0.1 to 1.0 wt % F−, i.e., fluoride ion, based on a 100 wt % total of the composition.
- In embodiments, the glass-ceramic composition can further comprise a source of 0.1 to 10 wt % B2O3, based on a 100 wt % total of the composition.
- In embodiments, the first crystalline phase and the second crystalline phase, in combination, can comprise a source of:
-
- 50 to 60 wt % SiO2,
- 1 to 3 wt % Al2O3,
- 2 to 6 wt % P2O3,
- 4 to 8 wt % CaO,
- 7.5 to 12.5 wt % Li2O,
- 0.5 to 2 wt % Na2O,
- 1 to 4 wt % ZrO2, and
- 0.2 to 0.8 wt % F−, based on a 100 wt % total of the composition.
- In embodiments, the abovementioned composition can be a preferred or a most preferred composition and can comprise, consist of, or consist essentially of, the abovementioned composition components.
- In embodiments, the disclosed bioactive compositions and articles can be a preferred or most preferred composition or article and can comprise, consist of, or consist essentially of, the disclosed bioactive composition or article.
- In embodiments, the disclosed methods of making and methods of using can be a preferred or most preferred method and can comprise, consist of, or consist essentially of, the disclosed methods.
- In embodiments, the composition can have a high strength of from 200 MPa to 500 MPa, for example, from at least 200 MPa, at least 300 MPa, or at least 400 MPa, including intermediate values and ranges.
- In embodiments, the composition can have a high fracture toughness of from 1.4 to 2.0 MPa·m1/2, for example, from at least 1.4, 1.6, 1.8, or 2.0 MPa·m1/2, including intermediate values and ranges.
- In embodiments, the composition can have a combination of high strength of from 200 MPa to 500 MPa, and high fracture toughness of from 1.4 to 2.0 MPa·m1/2.
- In embodiments, the composition can be prepared from a precursor glass composition comprising a source of, for example:
-
- 50 to 75 wt % SiO2,
- 1 to 5 wt % Al2O3,
- 1 to 8 wt % P2O3,
- 2 to 10 wt % CaO,
- 5 to 20 wt % Li2O,
- 0.5 to 5 wt % Na2O,
- 0.5 to 8 wt % ZrO2, and
- 0.1 to 1.0 wt % F−, based on a 100 wt % total of the composition.
- In embodiments, the abovementioned precursor glass composition does not change significantly upon ceramming.
- In embodiments, the disclosure provides a method of making the abovementioned glass-ceramic compositions comprising, for example:
-
- ceramming a precursor glass comprising a source of:
- 50 to 75 wt % SiO2,
- 1 to 5 wt % Al2O3,
- 1 to 8 wt % P2O3,
- 2 to 10 wt % CaO,
- 5 to 20 wt % Li2O,
- 0.5 to 5 wt % Na2O,
- 0.5 to 8 wt % ZrO2, and
- 0.1 to 1.0 wt % F−, based on a 100 wt % total of the composition, by heating the glass at 650 to 750° C. for 0.5 to 10 hrs, and then heating at 750 to 850° C. for 0.5 to 20 hrs.
- In embodiments, the method of making can further comprise, for example, ion exchanging the resulting glass-ceramic composition to create at least one compressive stress layer on at least one surface of the article to increase mechanical strength of the article.
- In embodiments, the disclosure provides a bioactive composition, comprising:
-
- a glass-ceramic comprised of:
- a first crystalline phase comprised of lithium disilicate; and
- a second crystalline phase selected from the group consisting of at least one of: wollastonite, fluoroapatite, cristobalite, β-quartz, lithiophosphate, or a combination thereof, and
- one or more live osteoblast cells, that is, a bioactive glass-ceramic including the disclosed composition and cells capable of synthesizing bone.
- a glass-ceramic comprised of:
- In embodiments, in the abovementioned bioactive composition the glass-ceramic composition can comprise, for example, a source of:
-
- 50 to 75 wt % SiO2,
- 1 to 5 wt % Al2O3,
- 1 to 8 wt % P2O3,
- 2 to 10 wt % CaO,
- 5 to 20 wt % Li2O,
- 0.5 to 5 wt % Na2O,
- 0.5 to 8 wt % ZrO2, and
- 0.1 to 1.0 wt % F−, based on a 100 wt % total of the composition.
- In embodiments, the glass-ceramic composition can comprise, for example, a source of:
-
- 50 to 60 wt/O SiO2,
- 1 to 3 wt % Al2O3,
- 2 to 6 wt % P2O3,
- 4 to 8 wt % CaO,
- 7.5 to 12.5 wt % Li2O,
- 0.5 to 2 wt % Na2O,
- 1 to 4 wt % ZrO2, and
- 0.2 to 0.8 wt % F−, based on a 100 wt % total of the composition.
- In embodiments, the abovementioned bioactive composition can further comprise, for example, a source of 0.1 to 10 wt % B2O3, based on a 100 wt % total of the composition.
- In embodiments, the disclosure provides a method of culturing osteoblast cells, i.e., a method of using the disclosed bioactive composition, comprising, for example:
-
- contacting the abovementioned bioactive composition with a suitable liquid medium.
- In embodiments, the glass-ceramic composition of the bioactive composition can be combined or contacted with the suitable liquid medium prior to being contacted with the live osteoblast cell(s).
- In embodiments, the contacting produces a proliferation of the osteoblast cells on the surface of the bioactive composition.
- In embodiments, the contacting produces a proliferation of the osteoblast cells in the suitable liquid medium, such as the culture medium of MC3T3 cells: i.e., alpha-MEM supplemented with 10% fetal bovine serum and 1 mM sodium pyruvate.
- In embodiments, the suitable liquid medium can include, for example, a simulated body fluid (SBF) composition. SBF is used for testing apatite formation activity of bioactive glasses/glass-ceramics. The disclosed bioactive glass-ceramics form in-situ a biologically active apatite layer (e.g., the mineral phase of bone and teeth) that can bond to bone and teeth, and can even bond to soft tissue. The potential applications of the disclosed bioactive glass-ceramics can include, for example, monolithic articles, composites, films, coating, or like forms, for use in repair of load-bearing bones, dental regeneration, treatment of dental hypersensitivity, artificial vertebrae, spinous spacers, intervertebral spacers, iliac spacers, granular fillers, scaffolds, middle-ear implant and in other types of small-bone replacement, wound healing, and like applications. The disclosed bioactive glass-ceramics are biocompatible with, for example, osteoblasts, keratinocytes, human umbilical vein endothelial cells (HUVEC), etc. (see for example, T. Kokubo et al., “How useful is SBF in predicting in vivo bone bioactivity?”, Biomaterials, 27[15] 2907-15 (2006)).
- In embodiments, the disclosed compositions and disclosed bioactive compositions can also have application in, for example: angiogenesis (HUVEC cells), wound healing (keratinocytes), bone tissue engineering (MC3T3 cells), and like applications.
- In embodiments, the disclosed composition is biocompatible with various cell types in various applications, and are biologically active (i.e., bioactive).
- In embodiments, the disclosed compositions and methods thereof are advantaged in several aspects, including for example:
-
- glass-ceramic compositions having a combination of high strength and high toughness;
- glass-ceramic compositions having excellent biocompatibility; and
- glass-ceramic compositions having a capability of supporting the growth and functionalization of osteoblastic cells.
- In embodiments, the disclosed bioactive glass-ceramic compositions can further comprise, for example, a form factor selected from a hollow microsphere, a solid microsphere, or a combination thereof, that is, where the glass composition has a particle shape, such as a sphere, an elongated sphere or egg-shape, a rod, or like geometries. Table 1 lists representative examples of the disclosed compositions. The ceramming cycle for all examples 1 to 15 was 700° C. for 2 hr and 800° C. for 4 hr.
-
TABLE 1 Example compositions (Ex. 7 to 15) and control compositions (Ex. C-1 to C-6). Oxides (wt %) C-11 C-2 C-3 C-4 C-5 C-6 7 8 9 10 11 12 13 14 15 SiO2 70 65 60 55 60 60 70 65 60 55 60 60 60 60 60 B2O3 0 0 0 0 0 0 0 0 0 0 0 0 2 4 6 Al2O3 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Li2O 12 12 12 12 15 12 12 12 12 12 15 12 12 12 12 Na2O 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 CaO 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 P2O5 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 ZrO2 2 2 2 2 2 4 2 2 2 2 2 4 2 2 2 F −0 0 0 0 0 0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Phase A A A B C D E E F G G H F F F assemblage2 Flexural — — — — — — 504 407 485 303 — — — — — strength (MPa) Fracture — — — — — — 1.8 1.9 2.2 2.2 — — — — — toughness (MPa•m1/2) 1C-# designation represents a control example (i.e., C- to C-6). 2Phase assemblage key: A = Lithium disilicate, cristobalite, wollastonite, ß-quartz, lithiophosphate. B = Lithium disilicate, wollastonite, lithiophosphate. C = Lithium disilicate, lithium metasilicate, wollastonite, lithiophospahte. D = Lithium disilicate, ß-quartz, lithiophospahte. E = Lithium disilicate, cristobalite, fluoroapatite, ß-quartz. F = Lithium disilicate, fluoroapatite, ß-quartz, lithiophosphate. G = Lithium disilicate, fluoroapatite, lithium metasilicate, ß-quartz. H = Lithium disilicate, fluoroapatite, ß-quartz. Sample Appearance: Samples of Examples 1 to 8 and 10 to 15 were translucent white; Example 9 was translucent/semi-transparent white. - In embodiments, the disclosed compositions can be free of (e.g., zero ppm or ppb), or substantially free of (e.g., trace amounts less than several ppm or ppb), at least one of, for example, K2O, K2CO3, Ca3(PO4)2, MgO, TiO2, As2O3, Sb2O3, or combinations or mixtures thereof.
- In embodiments, the disclosure provides precursor glass compositions that can be cerammed to produce glass-ceramics having excellent mechanical properties and biocompatibility. In embodiments, the disclosure provides glass-ceramics having high mechanical strength by forming an interlocking structure in the cerammed articles, which forces cracks to propagate along a tortuous path. Additionally, the presence of minor crystallite phases such as fluoroapatite and wollastonite in the disclosed compositions is beneficial to the growth, proliferation, and function of osteoblastic cell lines.
- In embodiments, the precursor glass or source glass can comprise, for example, 50 to 75 wt % SiO2, 1 to 5 wt % Al2O3, 5 to 20 wt % Li2O, 0.5 to 5 wt % Na2O, 0.5 to 8 wt % ZrO2, and 0.1 to 1.0 F− wt % (i.e., fluoride ion), based on a 100 wt % total of the composition. In embodiments, a more preferred precursor glass composition, can be, for example, 50 to 60 wt % SiO2, 1.0 to 3.0 wt % Al2O3, 0.1 to 4.0 wt % B2O3, 7.5 to 12.5 wt % Li2O, 0.5 to 2.0 wt % Na2O, 1.0 to 4.0 wt % ZrO2, and 0.2 to 0.8 wt % F− ion based on a 100 weight percentage total (see Table 1).
- In embodiments, the precursor glasses can be cerammed into glass-ceramic articles having high crystallinity of, for example, 80% or more, such as 80 to 95%. The major crystallite phases are comprised of lithium disilicate. The minor crystallite phases can be comprised of, for example, fluoroapatite, wollastonite, cristobalite, β-quartz, lithiophosphate, or mixtures thereof depending on composition targeted.
- Referring to the Figures,
FIG. 1 shows X-ray diffraction spectra ofexample compositions 7 to 10, where thereference numerals example compositions 7 to 10, respectively, in Table 1. The significant peaks are identified (with marker shapes) as: lithium disilicate (asterisk), lithium metasilicate (triangle), fluoroapatite (dot), beta-quartz (square), and cristobalite (diamond). All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. - In embodiments, the disclosed glass-ceramic articles composed of interlocking lithium disilicate can be easily obtained by ceramming precursor glasses at temperatures of from 700 to 900° C. for a period of time. A grain size of the lithium disilicate phase can be larger than 1 micrometer having a high aspect ratio that is typically formed in glass-ceramics.
FIGS. 2A to 2D show SEM images of polished surfaces inexample compositions 7 to 10 corresponding toFIGS. 2A, 2B, 2C, and 2D , respectively. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. Specimens were etched in 1% HF for one min prior to observation. - Although not bound by theory, it is believed that the presence of interlocking crystals can be a significant factor in developing toughening mechanisms including, for example, crack deflection and tortuous crack path, which mechanisms can contribute to the observed high fracture toughness and high flexural strength (Table 1). For example, a fracture toughness of over 1.5 MPa·m1/2 and a flexural strength of over 300 MPa can be achieved in selected glass-ceramic compositions.
- In embodiments, the disclosed glass-ceramic product or residual glass can be ion exchanged to create a compressive stress layer in the surface of a ware to further improve mechanical strength.
- In embodiments, excellent biocompatibility was demonstrated in the disclosed glass-ceramic compositions. Cell attachment was clearly observed through confocal images on the surfaces of
compositions 7 to 9. MC 3T3 cells were cultured one day, fixed with 4% formaldehyde, and then stained with Alexa Fluor 568 phalloidin and DAPI prior to the confocal imaging.FIGS. 3A to 3D show confocal SEM images of MC3T3 cell growth in the disclosedcompositions 7 to 10 corresponding toFIGS. 3A, 3B, 3C, and 3D , respectively. All specimens were cerammed using a cycle of 700° C. for 2 hr and then 800° C. for 4 hr. Cells were cultured one day, fixed with 4% formaldehyde, and then stained with Alexa Fluor 568 phalloidin and DAPI prior to the confocal imaging. - The ability of the disclosed glass-ceramics of
examples compositions 7 to 10 to support cell proliferation was demonstrated by the expression of DNA from the cultured cells for absolute levels (FIG. 5A ) and for relative levels (FIG. 5B ) with respect to a TCT control. MCT3 cells were cultured on glass-ceramic discs. On day 4 andday 7, cells were digested with the digestion buffer (125 microgm/mL papain, 2 mM L-cysteine, 2 mMM EDTA) at 65° C. for overnight, the dsDNA amount was measured using Quant-iT™ PicoGreen® dsDNA Kit (Thermo Fisher). The increase of DNA concentration with increasing culture time provided additional evidence of the excellent biocompatibility of the disclosed compositions. - In embodiments, the disclosed glass-ceramics can be manufactured using a thin rolling, a float, a casting process, and like methods; and scaffolds can be produced using, for example, rapid prototyping, polymer foam replication, particle sintering, and like methods. Glass-ceramics of desired forms can be used to support cell growth and hard tissue regeneration.
- In embodiments, the realized mechanical strength, biocompatibility, and biodegradation of the disclosed compositions can be influenced by the glass compositions. In embodiments, the disclosed glass compositions can further include, for example: SiO2 which serves as the primary glass-forming oxide for precursor glass and can function to stabilize the networking structure of glass and glass-ceramics. In embodiments, the concentration of SiO2 should be sufficiently high to form a lithium disilicate crystal phase when the precursor glass is heat treated to convert to a glass-ceramic (i.e., cerammed). However, the glasses can't contain too much SiO2 since the melting temperature (200 poise temperature) of pure SiO2 or high-SiO2 glasses is undesirably high. In embodiments, glass or glass-ceramic compositions can comprise, for example, 68 to 82 wt % SiO2, based on a 100 wt % total weight.
- In embodiments, the Al2O3 may also provide stabilization to the networking structure. Al2O3 is favorable to the improvement of mechanical properties and chemical durability. However, too much Al2O3 generally increases the viscosity of the melt and decreases the fraction of lithium disilicate crystals to an extent that no interlocking structure can be formed. The Al2O3 concentration is preferably maintained in a reasonable range of, for example, from 1 to 5 wt %.
- In embodiments, the addition of B2O3 can be beneficial to improved crack-resistance of the glass-ceramics, which is helpful for dental applications. Furthermore, a higher boron concentration can increase the degradation rate of the bioactive compositions, which property may be desired in applications such as bone regeneration.
- Li2O is another significant component in the disclosed precursor glass compositions. Li2O is advantageous for forming lithium disilicate crystal phases. Li2O is called for to have at least 8 wt % Li2O to obtain glass-ceramics having lithium disilicate as a predominant phase. However, when the Li2O content gets too high, such as greater than 15 wt %, the precursor glasses become very fluid with low resistivity making it difficult to melt or form.
- In embodiments, the disclosed glass and glass-ceramic compositions can include, for example, from 2 to 6 wt % P2O5, for example, as a nucleating agent to produce bulk nucleation. If the P2O5 concentration is too low, such as less than 2 wt %, the precursor glass does not crystallize. If the P2O5 concentration is too high, such as greater than 6 wt %, the devitrification upon cooling during precursor glass forming, can be difficult to control.
- In embodiments, divalent cation oxides, such as alkaline earth oxides, can also be used to improve the melting behavior and the bioactivity of the glass. For example, CaO was found to combine with P2O5 to form apatite, or with SiO2 to form wollastonite. Both apatite and wollastonite are known bioactive ceramics (see Hench, L. L., supra.).
- In embodiments, including Na2O in the precursor glass in an amount of from 0.1 to 5 wt % can reduce the melting temperature of the precursor glass, and can shorten the ceramming cycle. Furthermore, including Na2O in the precursor glass can also increase the thermal expansion after ceramming if a higher thermal expansion (i.e., CTE) is desired in the glass-ceramic articles.
- In embodiments, melting was accomplished at an elevated temperature, such as above 1300° C., to fuse the precursor glass materials. In embodiments, ceramming was the heat treatment of the melted glass that was used to crystallize the glass into a glass-ceramic material.
- The following Examples demonstrate making, use, and analysis of the disclosed compositions and methods in accordance with the above general procedures.
- Preparation of Control Examples C-1 to C-6 and Actual Example Glass-
Ceramic Compositions 7 to 15 Control and Actual Example Glass-Ceramic Compositions 1 to 15 listed in Table 1, and their respective glass source materials in the indicated amounts, including for example, silica, boric acid, alumina, lithium carbonate, sodium carbonate, limestone, spodumene, aluminum metaphosphate, were individually combined and melted in an electric furnace. Prior to melting, the precursor glass source materials were vigorously mixed in a plastic jar using a Turbula® mixer. Then the mixtures were transferred to a platinum crucible with an internal volume of approximately 650 cc and heated at 700° C. for 2 hr then 800° C. for 4 hr, and then the glass melt was poured on a steel plate, and annealed at 500° C. - Preparation of Glass-ceramic discs Glass-ceramic discs were prepared from cerammed parts. Precursor glass patties were cerammed in an electronic furnace using a cycle of 700° C. to 2 hr for nucleation and then 800° C. for 4 hr for crystal growth. After ceramming, the discs (12.5 mm in diameter×2.0 mm thick) were core-drilled using a diamond drill, and then ground and polished to a 1.0 micrometer finish using a CeO2 slurry. All finished discs were cleaned by sonicating in an ultrasonic sonicator for 10 min.
- METHOD OF ATTACHMENT AND GROWTH OF BONE CELLS WITH THE BIOACTIVE COMPOSITION OF Example 1 Glass-ceramic discs of Example 2 (made from compositions of the above working Example 1) were placed in wells of 24 well tissue culture treated microplates. Each composition has duplicate discs. MC 3T3 cells were then seeded (20K/2 mL) into the wells and some wells without any discs (Tissue Culture Treated (TCT) control). The microplates were cultured for 1, 4, or 7 days. Cells in the 1 day culture microplate were fixed with 4% formaldehyde, and then stained with Alexa Fluor 568 phalloidin and DAPI prior to the confocal imaging.
-
FIGS. 4A and 4 B show Day 1 attachment and proliferation of MC3T3 cells on disclosed bioactive glass-ceramic discs ofExample compositions -
FIGS. 5A and 5B show cell proliferation results for disclosedcompositions 7 to 10. Cells in the day 4 (D4) and day 7 (D7) culture plates were digested with the digestion buffer (125 microg/mL papain, 2 mM L-cysteine, 2 mM EDTA) at 65° C. for 16 hrs, the dsDNA amount was measured using Quant-iT™ PicoGreen® dsDNA Kit (Thermo Fisher). The increase of DNA concentration with increasing culture time provides additional evidence of their excellent biocompatibility. - MC3T3 cells were digested with papain and the amount of DNA was measured using a PicoGreen assay. D4 or D7 refers to Day 4 or Day 7 (as in “the 4th day or 7th day of cell culture”). TCT refers to a tissue culture treated microplate substrate available from Corning, Inc®. Glass-ceramic discs were placed in wells of 24 well tissue culture treated microplates. Each composition has duplicate discs. MC 3T3 cells were then seeded (20K/2 mL) into the wells and some wells without any discs (TCT control). The microplates were cultured for 4 or 7 days. On the day 4 and
day 7, cells were digested with a digestion buffer (D-PBS containing 125 microg/mL papain, 2 mM L-cysteine, 2 mMM EDTA) at 65° C. in humid environment with shaking (60 rpm) for 16 hrs. An attempt was made to remove the lysed DNA from glass-ceramic discs by pipetting digestion solution up and down on the discs. The collected digestion solution was briefly centrifuged to remove any remaining particles. The dsDNA amount in the supernatant was measured using Quant-iT™ PicoGreen® dsDNA Kit (Thermo Fisher) according to the manufacturer's instruction. - MC3T3E1 Subclone 14 (ATCC® CRL2594™)(see atcc.org/products/all/CRL-2594.aspx).
- Quant-iT™ PicoGreen® dsDNA Kit (Invitrogen, #P11496). This kit contains Quant-iT™ PicoGreen® dsDNA Reagent (10 vials, each containing 100 microL aliquots), 25 mL of 20×TE buffer, 1 mL of 100 microg/mL Lambda DNA (dsDNA standard), Papain (Sigma-Aldrich, #P4762-25MG), L-cysteine (Sigma-Aldrich, #C1276-10G), EDTA (Sigma-Aldrich, #E6511), D-PBS (Thermo Fisher, #14190), a shaker set to 65° C., and a plate reader.
- The disclosure has been described with reference to various specific embodiments and techniques. However, it should be understood that many variations and modifications are possible while remaining within the scope of the disclosure.
Claims (20)
1. A glass-ceramic article, comprising:
a first crystalline phase comprising lithium disilicate;
a second crystalline phase selected from a group consisting of: wollastonite, apatite, cristobalite, β-quartz, lithiophosphate, or a combination thereof; and
a glass-ceramic composition comprising, based on a 100 wt % total of the glass-ceramic composition:
50 to 75 wt % SiO2,
1 to 5 wt % Al2O3,
1 to 8 wt % P2O5,
up to 10 wt % CaO,
5 to 20 wt % Li2O,
up to 5 wt % Na2O,
greater than 0.5 wt % ZrO2, and
up to 10 wt % B2O3.
2. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition comprises, based on a 100 wt % total of the glass-ceramic composition:
50 to 60 wt % SiO2,
1 to 3 wt % Al2O3,
2 to 6 wt % P2O3,
4 to 8 wt % CaO,
7.5 to 12.5 wt % Li2O,
0.5 to 2 wt % Na2O, and
1 to 8 wt % ZrO2.
3. The glass-ceramic article of claim 1 , further comprising a compressive stress layer on at least one surface of the glass-ceramic article.
4. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition comprises, based on a 100 wt % total of the glass-ceramic composition, further comprising at least one of:
2 to 10 wt % CaO;
0.5 to 5 wt % Na2O;
0.1 to 10 wt % B2O3; or
combinations thereof.
5. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition comprises, based on a 100 wt % total of the glass-ceramic composition, 2 to 10 wt % CaO.
6. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition comprises, based on a 100 wt % total of the glass-ceramic composition, 0.5 to 5 wt % Na2O.
7. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition comprises, 0.1 to 10 wt % B2O3 based on a 100 wt % total of the glass-ceramic composition:
8. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition further comprises from 0.1 to 1.0 wt % F−, based on a 100 wt % total of the glass-ceramic composition.
9. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition has a fracture toughness greater than 1.5 MPa·m1/2.
10. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition has a fracture toughness of from 1.4 to 2.0 MPa·m1/2.
11. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition has a flexural strength greater than 300 MPa.
12. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition has a strength of from 200 MPa to 500 MPa.
13. The glass-ceramic article of claim 1 , wherein the glass-ceramic composition further comprises a crystallinity of greater than 80% by volume.
14. A method of making the glass-ceramic article of claim 1 , the method comprising:
ceramming a precursor glass mixture comprising, based on a 100 wt % total of the precursor glass mixture:
50 to 75 wt % SiO2,
1 to 5 wt % Al2O3,
1 to 8 wt % P2O5,
up to 10 wt % CaO,
5 to 20 wt % Li2O,
up to 5 wt % Na2O,
greater than 0.5 wt % ZrO2, and
up to 10 wt % B2O3, by heating the precursor glass mixture at 650° C. to 750° C. for from 0.5 hours to 10 hours and then heating at 750° C. to 850° C. for 0.5 hours to 20 hours; and
ion exchanging the resulting glass-ceramic composition to create at least one compressive stress layer on at least one surface of the glass-ceramic composition to increase mechanical strength,
wherein the glass-ceramic article further comprises a second crystalline phase selected from a group consisting of: wollastonite, apatite, cristobalite, β-quartz, lithiophosphate, or a combination thereof.
15. The method of claim 14 , wherein the precursor glass mixture comprises, based on a 100 wt % total of the precursor glass mixture:
50 to 60 wt % SiO2,
1 to 3 wt % Al2O3,
2 to 6 wt % P2O3,
4 to 8 wt % CaO,
7.5 to 12.5 wt % Li2O,
0.5 to 2 wt % Na2O,
1 to 8 wt % ZrO2, and
0.1 to 10 wt % B2O3.
16. The method of claim 14 , wherein the glass-ceramic composition further comprises a crystallinity of greater than 80% by volume.
17. The method of claim 14 , wherein the glass-ceramic composition comprises, based on a 100 wt % total of the glass-ceramic composition, further comprising at least one of:
2 to 10 wt % CaO;
0.5 to 5 wt % Na2O;
0.1 to 10 wt % B2O3; or
combinations thereof.
18. The method of claim 14 , wherein the precursor glass mixture comprises, based on a 100 wt % total of the precursor glass mixture, 2 to 10 wt % CaO.
19. The method of claim 14 , wherein the precursor glass mixture comprises, based on a 100 wt % total of the precursor glass mixture, 0.5 to 5 wt % Na2O.
20. The method of claim 14 , wherein the precursor glass mixture further comprises a source of 0.1 to 10 wt % B2O3, based on a 100 wt % total of the precursor glass mixture.
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US18/376,260 US20240026296A1 (en) | 2016-05-27 | 2023-10-03 | Lithium disilicate glass-ceramic compositions and methods thereof |
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6908521B2 (en) * | 2014-12-11 | 2021-07-28 | コーニング インコーポレイテッド | X-ray-induced coloring in glass or glass-ceramic articles |
US10059621B2 (en) | 2016-05-27 | 2018-08-28 | Corning Incorporated | Magnetizable glass ceramic composition and methods thereof |
US10676713B2 (en) | 2016-05-27 | 2020-06-09 | Corning Incorporated | Bioactive borophosphate glasses |
US10751367B2 (en) | 2016-05-27 | 2020-08-25 | Corning Incorporated | Bioactive glass microspheres |
US20170342383A1 (en) | 2016-05-27 | 2017-11-30 | Corning Incorporated | Lithium disilicate glass-ceramic compositions and methods thereof |
US10647962B2 (en) | 2016-05-27 | 2020-05-12 | Corning Incorporated | Bioactive aluminoborate glasses |
CN111433165A (en) | 2017-11-28 | 2020-07-17 | 康宁股份有限公司 | High liquidus viscosity bioactive glass |
CN111405913A (en) | 2017-11-28 | 2020-07-10 | 康宁股份有限公司 | Bioactive glass compositions and dentinal hypersensitivity repair |
EP3717428A1 (en) | 2017-11-28 | 2020-10-07 | Corning Incorporated | Bioactive borate glass and methods thereof |
CN111417601A (en) | 2017-11-28 | 2020-07-14 | 康宁股份有限公司 | Chemically strengthened bioactive glass-ceramics |
JP7079851B2 (en) * | 2017-12-01 | 2022-06-02 | シーディージーエム グラス カンパニー リミテッド | Crystallized glass and its substrate |
DE102018104839A1 (en) * | 2018-03-02 | 2019-09-05 | Friedmar Hütter | ear implant |
WO2020112396A2 (en) | 2018-11-26 | 2020-06-04 | Ocv Intellectual Capital, Llc | High performance fiberglass composition with improved specific modulus |
DK3887329T3 (en) | 2018-11-26 | 2024-04-29 | Owens Corning Intellectual Capital Llc | HIGH PERFORMANCE FIBERGLASS COMPOSITION WITH IMPROVED COEFFICIENT OF ELASTICITY |
US20220089473A1 (en) * | 2019-01-16 | 2022-03-24 | Corning Incorporated | Glass-ceramics based on lithium disilicate, zircon, and apatite |
JP6974600B2 (en) | 2019-03-06 | 2021-12-01 | 株式会社オハラ | Inorganic composition articles and crystallized glass |
CN115996897A (en) * | 2020-06-29 | 2023-04-21 | 康宁股份有限公司 | Glass ceramic composition and method for producing same |
GB202010237D0 (en) * | 2020-07-03 | 2020-08-19 | King S College London | Dental material |
KR102446072B1 (en) * | 2020-09-28 | 2022-09-23 | 주식회사 하스 | Dental bulk block for cad/cam machining process and manufacturing method of the same |
EP4049981A1 (en) * | 2021-02-24 | 2022-08-31 | Ivoclar Vivadent AG | Glass ceramic with quartz mixed crystal phase |
US20220402809A1 (en) * | 2021-06-18 | 2022-12-22 | Corning Incorporated | Precursor glasses and transparent glass-ceramic articles formed therefrom and having improved mechanical durability |
CN116477843A (en) * | 2022-01-17 | 2023-07-25 | 荣耀终端有限公司 | Glass ceramic, reinforced glass, preparation method of glass ceramic, shell of electronic equipment, display screen of electronic equipment and electronic equipment |
JP2024045871A (en) * | 2022-09-22 | 2024-04-03 | 株式会社オハラ | crystallized glass |
Family Cites Families (170)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2532386A (en) | 1949-09-27 | 1950-12-05 | Corning Glass Works | Colored phosphate glass |
NL232500A (en) | 1957-10-22 | |||
US2926665A (en) * | 1957-12-12 | 1960-03-01 | Geraldine E Seese | Bandaging garment |
US2987339A (en) | 1960-01-27 | 1961-06-06 | Cullen Friestedt Company | Articulated lifter |
BE618737A (en) | 1961-06-12 | |||
US3323888A (en) | 1964-03-17 | 1967-06-06 | Cataphote Corp | Method for manufacturing glass beads |
US3778335A (en) | 1971-09-02 | 1973-12-11 | Corning Glass Works | Sodium aluminosilicate glass article strengthened by a surface compressive stress layer |
US4126437A (en) | 1976-12-02 | 1978-11-21 | Xerox Corporation | Magnetic glass carrier materials |
US4083727A (en) | 1977-01-07 | 1978-04-11 | Corning Glass Works | Glass-ceramics with magnetic surface films |
US4084972A (en) | 1977-01-07 | 1978-04-18 | Corning Glass Works | Glass-ceramics with metallic iron surfaces |
US4140645A (en) | 1978-06-12 | 1979-02-20 | Corning Glass Works | Glasses and glass-ceramics suitable for induction heating |
GB2035290B (en) | 1978-11-24 | 1982-11-10 | Standard Telephones Cables Ltd | Glass compositions and cements incorporating such compositions |
US4233169A (en) | 1979-04-13 | 1980-11-11 | Corning Glass Works | Porous magnetic glass structure |
US4323056A (en) | 1980-05-19 | 1982-04-06 | Corning Glass Works | Radio frequency induced hyperthermia for tumor therapy |
US4391646A (en) | 1982-02-25 | 1983-07-05 | Minnesota Mining And Manufacturing Company | Glass bubbles of increased collapse strength |
JPS60210546A (en) | 1984-04-02 | 1985-10-23 | Ngk Spark Plug Co Ltd | Crystallized glass for crown |
GB8612387D0 (en) | 1986-05-21 | 1986-07-16 | Univ Sheffield | Glass ceramics |
KR920001501B1 (en) | 1987-09-01 | 1992-02-15 | 가부시기가이샤 히다찌세이사구쇼 | Black matrix color picture tube and the method of the same |
US4889707A (en) | 1988-01-29 | 1989-12-26 | The Curators Of The University Of Missouri | Composition and method for radiation synovectomy of arthritic joints |
US5217928A (en) | 1988-08-24 | 1993-06-08 | Potters Industries, Inc. | Hollow glass spheres |
US5196381A (en) | 1990-01-16 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Metaphosphate glass composition |
IT1240938B (en) | 1990-02-08 | 1993-12-27 | S.E.I.P.I. Societa' Esportazione Importazione Prodotti Industriali | BIOACTIVE GLASS COMPOSITION FOR BONE IMPLANTS AND PRODUCTS OBTAINED WITH SUCH A COMPOSITION OR THAT INCLUDE IT |
US5153070A (en) | 1990-08-01 | 1992-10-06 | Corning Incorporated | Coated refractory article and method |
US5252523A (en) | 1991-10-09 | 1993-10-12 | Corning Incorporated | Bioabsorbable chlorophosphate glasses and bioabsorbable glass-polymer blends made therefrom |
US5876452A (en) | 1992-02-14 | 1999-03-02 | Board Of Regents, University Of Texas System | Biodegradable implant |
EP0672117A4 (en) * | 1992-08-13 | 1996-06-12 | Univ Pennsylvania | BIOACTIVE MATERIAL TEMPLATE FOR -i(IN VITRO) SYNTHESIS OF BONE TISSUE. |
SK45594A3 (en) | 1992-08-20 | 1994-09-07 | Saint Gobain Isover | Method of producing mineral wool, and mineral wool produced thereby |
US5648124A (en) | 1993-07-09 | 1997-07-15 | Seradyn, Inc. | Process for preparing magnetically responsive microparticles |
US5849816A (en) | 1994-08-01 | 1998-12-15 | Leonard Pearlstein | Method of making high performance superabsorbent material |
DE4428851C2 (en) | 1994-08-04 | 2000-05-04 | Diagnostikforschung Inst | Nanoparticles containing iron, their production and application in diagnostics and therapy |
US6254981B1 (en) | 1995-11-02 | 2001-07-03 | Minnesota Mining & Manufacturing Company | Fused glassy particulates obtained by flame fusion |
DE69614721T2 (en) | 1995-11-14 | 2002-07-04 | Corning Inc., Corning | SEPARATE NON-CRYSTALLINE OPAL GLASSES |
US5674790A (en) | 1995-12-15 | 1997-10-07 | Corning Incorporated | Strengthening glass by ion exchange |
PL328149A1 (en) | 1996-01-29 | 1999-01-18 | Univ Maryland | Bioactive glass compositions and therapeutic methods employing bioactive glass |
WO1997027148A1 (en) | 1996-01-29 | 1997-07-31 | Usbiomaterials Corporation | Bioactive glass compositions and methods of treatment using bioactive glass |
US5735942A (en) | 1996-02-07 | 1998-04-07 | Usbiomaterials Corporation | Compositions containing bioactive glass and their use in treating tooth hypersensitivity |
US5707715A (en) | 1996-08-29 | 1998-01-13 | L. Pierre deRochemont | Metal ceramic composites with improved interfacial properties and methods to make such composites |
US6323549B1 (en) | 1996-08-29 | 2001-11-27 | L. Pierre deRochemont | Ceramic composite wiring structures for semiconductor devices and method of manufacture |
US5834008A (en) | 1996-09-19 | 1998-11-10 | U.S. Biomaterials Corp. | Composition and method for acceleration of wound and burn healing |
US6756060B1 (en) | 1996-09-19 | 2004-06-29 | Usbiomaterials Corp. | Anti-inflammatory and antimicrobial uses for bioactive glass compositions |
AU4571097A (en) | 1996-10-09 | 1998-05-05 | Takeda Chemical Industries Ltd. | A method for producing a microparticle |
WO1998047830A1 (en) | 1997-04-18 | 1998-10-29 | Minnesota Mining And Manufacturing Company | Transparent beads and their production method |
US6280863B1 (en) * | 1997-06-12 | 2001-08-28 | Ivoclar Ag | Translucent apatite glass ceramic |
DE19725555A1 (en) * | 1997-06-12 | 1998-12-24 | Ivoclar Ag | Translucent apatite glass-ceramic |
US6034014A (en) | 1997-08-04 | 2000-03-07 | Owens Corning Fiberglas Technology, Inc. | Glass fiber composition |
GB9811661D0 (en) | 1998-06-01 | 1998-07-29 | Giltech Ltd | Compositions |
US6802894B2 (en) | 1998-12-11 | 2004-10-12 | Jeneric/Pentron Incorporated | Lithium disilicate glass-ceramics |
EP2338448A3 (en) | 1998-09-10 | 2013-12-11 | USBiomaterials Corporation | Anti-inflammatory and antimicrobial uses for bioactive glass |
US6214471B1 (en) | 1998-11-03 | 2001-04-10 | Corning Incorporated | Glasses compatible with aluminum |
JP2001010843A (en) | 1999-04-30 | 2001-01-16 | Ohara Inc | Crystalline low-melting glass and sealing composition |
IT1313655B1 (en) | 1999-09-30 | 2002-09-09 | Techint Spa | GLASS FIBER COMPOSITION. |
US6328990B1 (en) | 1999-11-12 | 2001-12-11 | The Trustees Of The University Of Pennsylvania | Bioactive, degradable composite for tissue engineering |
JP2001247333A (en) | 1999-12-28 | 2001-09-11 | Ishizuka Glass Co Ltd | Glass composition for imparting antimicrobial properties, antimicrobial fiber, antimicrobial spun yarn and antimicrobial fabric |
US6306423B1 (en) | 2000-06-02 | 2001-10-23 | Allergan Sales, Inc. | Neurotoxin implant |
JP4323707B2 (en) | 2000-10-25 | 2009-09-02 | 富士通マイクロエレクトロニクス株式会社 | Flash memory defect management method |
US7597900B2 (en) | 2001-03-27 | 2009-10-06 | Schott Ag | Tissue abrasives |
US20040166172A1 (en) | 2001-03-27 | 2004-08-26 | Coni Rosati | Bioctive tissue abrasives |
DE10293767B4 (en) | 2001-08-22 | 2017-06-08 | Schott Ag | Disinfectant glass powder with antimicrobial, anti-inflammatory, wound-healing effect and its use |
DE10141117A1 (en) | 2001-08-22 | 2003-03-13 | Schott Glas | Antimicrobial silicate glass and its use |
JP2005501113A (en) | 2001-08-22 | 2005-01-13 | カール−ツァイス−スティフツング | Antibacterial glass powder that suppresses inflammation and heals wounds, and method of using the same |
EP1463688B1 (en) | 2001-12-12 | 2005-07-13 | Schott Ag | Use of an antimicrobial glass ceramic for dental care and oral hygiene |
JP2005511471A (en) | 2001-12-12 | 2005-04-28 | ロックウール インターナショナル アー/エス | Fiber and method for producing the same |
WO2004084851A2 (en) | 2003-03-24 | 2004-10-07 | Exa Sa | A treatment composition |
DE10203629A1 (en) | 2002-01-30 | 2003-07-31 | Ulrich Zimmermann | Device and method for producing microcapsules and improved microcapsule |
JP2003249763A (en) | 2002-02-25 | 2003-09-05 | Fujitsu Ltd | Multilayer interconnection board and manufacturing method thereof |
DE10214273A1 (en) | 2002-03-28 | 2003-10-23 | Schott Glas | Use of glass and/or glass ceramic powder and/or fiber for time- and quantity-controlled ion release is useful cosmetic or medicinal formulation as skin care cream and for healing or covering wound and treating chronic wound |
JP5078227B2 (en) | 2002-11-15 | 2012-11-21 | カラー アクセス,インコーポレイティド | Transparent hiding cosmetic composition |
US20050118236A1 (en) | 2002-12-03 | 2005-06-02 | Gentis Inc. | Bioactive, resorbable scaffolds for tissue engineering |
EP1597211A2 (en) | 2003-02-25 | 2005-11-23 | Schott AG | Antimicrobial phosphate glass |
JP4293806B2 (en) | 2003-02-28 | 2009-07-08 | 石塚硝子株式会社 | Antibacterial imparting glass composition and antibacterial polymer composite material using the same |
GB0310673D0 (en) | 2003-05-09 | 2003-06-11 | Givaudan Sa | Alginate matrix particles |
JP2004359754A (en) | 2003-06-03 | 2004-12-24 | Ishizuka Glass Co Ltd | Antimicrobial resin composition and its molding |
US8444756B2 (en) * | 2003-08-07 | 2013-05-21 | Ivoclar Vivadent Ag | Lithium silicate materials |
HU227595B1 (en) | 2003-08-07 | 2011-09-28 | Mta | Metal complexes of polygalacturonic acid and their production |
DE10336913C9 (en) | 2003-08-07 | 2019-02-21 | Ivoclar Vivadent Ag | Use of a lithium silicate material |
FR2867075B1 (en) | 2004-03-03 | 2006-07-14 | Ethypharm Sa | PROCESS FOR PREPARING CALIBRATED BIODEGRADABLE MICROSPHERES |
DE102004011520A1 (en) | 2004-03-08 | 2005-10-06 | Schott Ag | Antimicrobial refractive index adapted phosphate glass |
DE102004013455B3 (en) | 2004-03-18 | 2005-09-08 | Ivoclar Vivadent Ag | Apatite glass-ceramic useful for making dental materials comprises a glass phase and a phosphate- and fluorine-free silicate-based oxyapatite phase |
US7771742B2 (en) | 2004-04-30 | 2010-08-10 | Allergan, Inc. | Sustained release intraocular implants containing tyrosine kinase inhibitors and related methods |
DE102004026432A1 (en) | 2004-05-29 | 2005-12-22 | Schott Ag | Glass compositions as antimicrobial additive for dental materials and their use |
FR2873683B1 (en) | 2004-07-27 | 2007-06-15 | Inst Nat Sciences Appliq | POROUS BIOVERRE AND PROCESS FOR PREPARING THE SAME |
DE202004014053U1 (en) | 2004-09-07 | 2004-11-11 | Deep Colours! Gmbh | tattoo |
US20060127427A1 (en) | 2004-12-15 | 2006-06-15 | Vernice Joseph J | Surface coated abrasive material for cosmetic products |
DE102005001078A1 (en) | 2005-01-08 | 2006-07-20 | Schott Ag | Glass powder, in particular biologically active glass powder and process for the production of glass powder, in particular biologically active glass powder |
US9326995B2 (en) | 2005-04-04 | 2016-05-03 | The Regents Of The University Of California | Oxides for wound healing and body repair |
US7989065B2 (en) | 2005-05-20 | 2011-08-02 | Seradyn, Inc. | Magnetically-responsive microparticles with improved response times |
DE102005026269A1 (en) | 2005-06-08 | 2006-12-14 | Ivoclar Vivadent Ag | Dental glass-ceramics |
JP4226574B2 (en) | 2005-06-27 | 2009-02-18 | 株式会社ノリタケカンパニーリミテド | Glass composition having acid resistance |
JP2007039269A (en) | 2005-08-02 | 2007-02-15 | Asahi Glass Co Ltd | Glass for covering electrode, and plasma display device |
DE102005038070A1 (en) | 2005-08-10 | 2007-03-15 | Henkel Kgaa | Detergents and cleaners with well soluble capsules |
WO2007022264A2 (en) | 2005-08-15 | 2007-02-22 | The Regents Of The University Of California | Oxides for wound healing and body repair |
KR101024417B1 (en) | 2006-06-07 | 2011-03-23 | 가부시키가이샤 피노레 | Mixed antibacterial glass |
GB0612028D0 (en) | 2006-06-16 | 2006-07-26 | Imp Innovations Ltd | Bioactive glass |
WO2008000888A2 (en) | 2006-06-28 | 2008-01-03 | Vivoxid Oy | Implant containing a source of oxygen |
US20090324668A1 (en) | 2006-06-28 | 2009-12-31 | Ilkka Kangasniemi | Implant, its uses and methods for making it |
US9539062B2 (en) * | 2006-10-16 | 2017-01-10 | Natural Dental Implants, Ag | Methods of designing and manufacturing customized dental prosthesis for periodontal or osseointegration and related systems |
US8288344B2 (en) | 2007-03-15 | 2012-10-16 | Musculoskeletal Transplant Foundation | Ceramic composition for filling bone defects |
EP2030957A1 (en) | 2007-08-28 | 2009-03-04 | Corning Incorporated | Fugitive pore former for porous ceramic articles |
WO2009062254A1 (en) | 2007-11-14 | 2009-05-22 | The University Of Queensland | Device and method for preparing microparticles |
US20090258778A1 (en) | 2008-04-11 | 2009-10-15 | James R., Glidewell Dental Ceramics, Inc. | Lithium silicate glass ceramic for fabrication of dental appliances |
US9241879B2 (en) | 2008-04-11 | 2016-01-26 | James R. Glidewell Dental Ceramics, Inc. | Lithium silicate glass ceramic for fabrication of dental appliances |
JP2011523927A (en) * | 2008-05-27 | 2011-08-25 | インペリアル イノベーションズ リミテッド | Method for producing porous scaffolds from sinterable glass |
CN101596326A (en) * | 2008-06-06 | 2009-12-09 | 华东理工大学 | A kind of borate biological microcrystalline glass and its production and application |
CN101407373B (en) | 2008-11-18 | 2011-12-28 | 湖北顶盛科技发展有限公司 | Strontium-reinforced bioactivity glass, production method there and use in tooth-cleaning products |
TWI391148B (en) | 2009-04-01 | 2013-04-01 | Colgate Palmolive Co | Non-aqueous dentifrice composition with bioacceptable and bioactive glass and methods of use and manufacture thereof |
EP2243749B1 (en) | 2009-04-23 | 2015-04-08 | PURAC Biochem BV | Resorbable and biocompatible fibre glass compositions and their uses |
CN101704632B (en) | 2009-11-30 | 2012-08-29 | 中国建材国际工程有限公司 | Preparation method of high-strength low-density hollow glass bead |
US20110152057A1 (en) | 2009-12-21 | 2011-06-23 | Gang Qi | Hollow microspheres |
US8173154B2 (en) | 2010-01-06 | 2012-05-08 | The Curators Of The University Of Missouri | Boron trioxide glass-based fibers and particles in dressings, sutures, surgical glue, and other wound care compositions |
EP2386525A1 (en) | 2010-05-13 | 2011-11-16 | Universitat Politècnica de Catalunya | Nanostructured material comprising a biocompatible calcium phosphate glass, sol-gel process for its preparation and medical use thereof |
US20160145567A1 (en) | 2010-05-27 | 2016-05-26 | Corning Incorporated | Cell culture article and methods thereof |
GB201010758D0 (en) | 2010-06-25 | 2010-08-11 | Queen Mary & Westfield College | Bioactive glass composition |
DE102010034083A1 (en) | 2010-08-12 | 2012-02-16 | Süd-Chemie AG | Magnetic glass particles for use in biogas plants, fermentation and separation processes |
CN101938877B (en) | 2010-09-19 | 2013-02-27 | 无锡力芯微电子股份有限公司 | LED driving circuit |
US8883663B2 (en) * | 2010-11-30 | 2014-11-11 | Corning Incorporated | Fusion formed and ion exchanged glass-ceramics |
KR101262121B1 (en) * | 2010-12-27 | 2013-05-14 | 주식회사 하스 | Manufacturing method of high strength glass ceramics for teeth |
US20140079642A1 (en) | 2011-01-24 | 2014-03-20 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd | Nanoparticles based for dermal and systemic delivery of drugs |
PT105617A (en) | 2011-04-05 | 2012-10-08 | Univ Aveiro | COMPOSITION OF BIOACTIVE GLASS, ITS USE AND RESPECTIVE METHOD OF OBTAINING |
CA2839953C (en) | 2011-06-20 | 2017-02-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US20120321567A1 (en) | 2011-06-20 | 2012-12-20 | Denis Alfred Gonzales | Liquid cleaning and/or cleansing composition |
GB201113754D0 (en) | 2011-08-09 | 2011-09-21 | Glaxo Group Ltd | Composition |
US20140000891A1 (en) | 2012-06-21 | 2014-01-02 | Self-Suspending Proppant Llc | Self-suspending proppants for hydraulic fracturing |
ES2568249T3 (en) | 2011-10-14 | 2016-04-28 | Ivoclar Vivadent Ag | Vitroceramic glass and lithium silicate glass with divalent metal oxide |
ES2562338T3 (en) | 2011-10-14 | 2016-03-03 | Ivoclar Vivadent Ag | Vitroceramic glass and lithium silicate glass with monovalent metal oxide |
CN102430149A (en) | 2011-11-18 | 2012-05-02 | 华东理工大学 | Phosphate glass fiber/chitosan composite material |
CN104039729B (en) * | 2012-01-20 | 2016-12-07 | 斯特劳曼控股公司 | Prosthetic element |
CN102526797B (en) | 2012-02-08 | 2013-10-30 | 同济大学 | Preparation method of high-strength biological glass bone bracket with regular-hole distribution |
KR20130112422A (en) | 2012-04-04 | 2013-10-14 | 이운덕 | Bike pedal cover for the protection of vehicle's rear |
KR20130112433A (en) | 2012-04-04 | 2013-10-14 | 주식회사 케이씨씨 | A composition for preparing glass wool and a biosoluble glass wool prepared therefrom |
EP2844213B1 (en) | 2012-05-04 | 2019-12-04 | Ivoclar Vivadent AG | Lithium disilicate apatite glass ceramic |
PT2668967E (en) | 2012-05-30 | 2014-07-30 | Skulle Implants Oy | An implant |
MX2015000810A (en) | 2012-07-19 | 2015-06-05 | Relypsa Inc | Compositions comprising crosslinked cation-binding polymers. |
JP6008278B2 (en) | 2012-07-24 | 2016-10-19 | パナソニックIpマネジメント株式会社 | Lighting device, lighting apparatus using the same, and lighting system |
US20140026916A1 (en) | 2012-07-25 | 2014-01-30 | College Of William And Mary | Method for Reducing Marine Pollution Using Polyhydroxyalkanoate Microbeads |
ES2688381T3 (en) | 2012-09-28 | 2018-11-02 | Stelo Technologies | Methods for making silver nanoparticles and their applications |
EP2931376B1 (en) | 2012-12-17 | 2017-07-26 | Unilever N.V. | Topical composition |
US20140212469A1 (en) | 2013-01-28 | 2014-07-31 | Missouri University Of Science And Technology | Surface functional bioactive glass scaffold for bone regeneration |
US20140219941A1 (en) | 2013-02-06 | 2014-08-07 | U.S. Cosmetic Corporation | Cosmetic powder coated with alginic acid and methods of making the same |
EP2969985A4 (en) | 2013-03-14 | 2017-01-11 | Novabone Products, LLC | Compositions and methods for manufacturing sol-gel derived bioactive borophosphate glasses for medical applicatons |
CA2905728A1 (en) | 2013-03-14 | 2014-09-25 | Novabone Products, Llc | Sodium containing sol-gel derived bioactive glasses and uses thereof including hemostasis |
EP2792345B1 (en) | 2013-04-15 | 2019-10-09 | Ivoclar Vivadent AG | Lithium silicate glass ceramic and glass with caesium oxide content |
CN103172263B (en) | 2013-04-16 | 2015-03-18 | 中国地质科学院 | Biological microcrystalline glass prepared by utilizing phosphate tailings and preparation method thereof |
US9359244B2 (en) | 2013-05-21 | 2016-06-07 | Colorado School Of Mines | Alumina-rich glasses and methods for making the same |
CN103449725B (en) | 2013-08-23 | 2016-03-30 | 四川大学 | A kind of biological activated glass ceramic material and preparation method thereof and the application in oral care implement |
US9701573B2 (en) | 2013-09-06 | 2017-07-11 | Corning Incorporated | High strength glass-ceramics having lithium disilicate and beta-spodumene structures |
US10117668B2 (en) | 2013-10-08 | 2018-11-06 | The Spectranetics Corporation | Balloon catheter with non-deployable stent having improved stability |
KR101524482B1 (en) * | 2013-10-14 | 2015-06-02 | 주식회사 하스 | Glass-ceramics or Lithium silicate glass for Zirconia overlaying materials and preparation method thereof |
EP2868634B1 (en) * | 2013-11-05 | 2021-07-07 | Ivoclar Vivadent AG | Lithium disilicate apatite glass ceramic with transition metal oxide |
JP2017505824A (en) | 2014-02-17 | 2017-02-23 | ザ プロクター アンド ギャンブル カンパニー | Skin cleansing composition comprising biodegradable abrasive particles |
US9622483B2 (en) | 2014-02-19 | 2017-04-18 | Corning Incorporated | Antimicrobial glass compositions, glasses and polymeric articles incorporating the same |
US9878940B2 (en) | 2014-02-21 | 2018-01-30 | Corning Incorporated | Low crystallinity glass-ceramics |
CN103979796B (en) | 2014-05-19 | 2016-08-24 | 白银金奇化工科技有限公司 | A kind of high intensity hollow glass micropearl and preparation method thereof |
EP3149985A1 (en) | 2014-06-02 | 2017-04-05 | Antique Books Inc. | Advanced proof of knowledge authentication |
EP3151873B1 (en) | 2014-06-09 | 2020-03-11 | The Royal Institution for the Advancement of Learning / McGill University | Borate-glass biomaterials |
EP3157461B1 (en) | 2014-06-23 | 2019-12-18 | 3M Innovative Properties Company | Process for producing a sintered lithium disilicate glass ceramic dental restoration |
CN104108883B (en) * | 2014-08-11 | 2019-03-08 | 中国地质大学(北京) | A kind of high intensity lithium bisilicate glass ceramics and preparation method thereof |
KR101648175B1 (en) * | 2014-08-29 | 2016-08-16 | 주식회사 하스 | Cristobalite crystal-containing lithium disilicate glass-ceramics with high strength and esthetics and preparation method thereof |
ES2840674T3 (en) * | 2014-10-08 | 2021-07-07 | Corning Inc | High-strength glass-ceramics that have lithium silicate and petalite structures |
BR112017011899A2 (en) | 2014-12-05 | 2018-07-03 | Augusta University Research Institute, Inc. | glass composites for cosmetic, biomedical and tissue enhancement applications |
DE102015108171A1 (en) | 2015-05-22 | 2016-11-24 | Degudent Gmbh | Process for increasing the strength of shaped bodies consisting of lithium silicate glass-ceramic |
CN105236745A (en) | 2015-08-27 | 2016-01-13 | 陕西科技大学 | Ferromagnetic Fe3O4 nano micro-crystal glass and preparation method thereof |
CN105819697B (en) | 2016-03-29 | 2019-03-01 | 中材科技股份有限公司 | A kind of bio-compatible phosphate base continuous glass fibre and fabric prepared therefrom |
US20170342383A1 (en) | 2016-05-27 | 2017-11-30 | Corning Incorporated | Lithium disilicate glass-ceramic compositions and methods thereof |
US20170340527A1 (en) | 2016-05-27 | 2017-11-30 | Corning Incorporated | Biodegradable microbeads |
US10059621B2 (en) | 2016-05-27 | 2018-08-28 | Corning Incorporated | Magnetizable glass ceramic composition and methods thereof |
US10647962B2 (en) | 2016-05-27 | 2020-05-12 | Corning Incorporated | Bioactive aluminoborate glasses |
US10676713B2 (en) | 2016-05-27 | 2020-06-09 | Corning Incorporated | Bioactive borophosphate glasses |
US10751367B2 (en) | 2016-05-27 | 2020-08-25 | Corning Incorporated | Bioactive glass microspheres |
CN107028770B (en) | 2017-03-07 | 2020-04-17 | 中国人民解放军第四军医大学 | Dentin reactive monomer mixture and preparation method thereof, polycarboxy oligomer and preparation method thereof, and dental composite resin bonding system |
US10624994B2 (en) | 2017-08-30 | 2020-04-21 | King Abdulaziz University | Borate bioactive glass and methods of use for dentin and enamel restoration |
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- 2017-05-25 EP EP17728385.0A patent/EP3464204B1/en active Active
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CN109311731A (en) | 2019-02-05 |
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US20170342383A1 (en) | 2017-11-30 |
KR20230127368A (en) | 2023-08-31 |
KR20190003780A (en) | 2019-01-09 |
KR102420123B1 (en) | 2022-07-12 |
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US20190048318A1 (en) | 2019-02-14 |
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