JP6652941B2 - 固有の耐損傷性を有する白色不透明のβ−スポジュメンガラスセラミック物品及びその製造方法 - Google Patents
固有の耐損傷性を有する白色不透明のβ−スポジュメンガラスセラミック物品及びその製造方法 Download PDFInfo
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- JP6652941B2 JP6652941B2 JP2016575380A JP2016575380A JP6652941B2 JP 6652941 B2 JP6652941 B2 JP 6652941B2 JP 2016575380 A JP2016575380 A JP 2016575380A JP 2016575380 A JP2016575380 A JP 2016575380A JP 6652941 B2 JP6652941 B2 JP 6652941B2
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- 239000002241 glass-ceramic Substances 0.000 title claims description 205
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims description 115
- 229910052644 β-spodumene Inorganic materials 0.000 title claims description 113
- 238000004519 manufacturing process Methods 0.000 title claims description 7
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- 239000000203 mixture Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 50
- 238000002425 crystallisation Methods 0.000 claims description 39
- 230000008025 crystallization Effects 0.000 claims description 39
- 238000005342 ion exchange Methods 0.000 claims description 39
- 230000006911 nucleation Effects 0.000 claims description 33
- 238000010899 nucleation Methods 0.000 claims description 33
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 32
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 229910052796 boron Inorganic materials 0.000 claims description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 230000000977 initiatory effect Effects 0.000 claims description 20
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 9
- HYFJXBYGHMZZPQ-UHFFFAOYSA-N boron(1+) Chemical compound [B+] HYFJXBYGHMZZPQ-UHFFFAOYSA-N 0.000 claims description 8
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- -1 boron cations Chemical class 0.000 claims description 6
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- 239000011734 sodium Substances 0.000 description 28
- 239000013078 crystal Substances 0.000 description 24
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- 150000002500 ions Chemical class 0.000 description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 12
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- 229910052810 boron oxide Inorganic materials 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
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- 238000000137 annealing Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
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- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 229910000174 eucryptite Inorganic materials 0.000 description 3
- XSETZKVZGUWPFM-UHFFFAOYSA-N magnesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Ti+4] XSETZKVZGUWPFM-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
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- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052642 spodumene Inorganic materials 0.000 description 2
- 210000003813 thumb Anatomy 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 235000003166 Opuntia robusta Nutrition 0.000 description 1
- 244000218514 Opuntia robusta Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 239000006092 crystalline glass-ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004293 potassium hydrogen sulphite Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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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
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- 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
- 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
- C03C10/0054—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 PbO, SnO2, B2O3
-
- 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
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C2204/00—Glasses, glazes or enamels with special properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
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Description
[Al2O3]のモルに対する[Li2O+Na2O+K2O+MgO+ZnO]のモル合計の比は、約0.8から約1.5の範囲内でありうる。
(1)1:1:4.5〜1:1:8又は、代替的に1:1:4.5〜1:1:7の範囲のLi2O:Al2O3:SiO2比を示し、結晶相の少なくとも70質量%を構成する、β−スポジュメン固溶体;
(2)少なくとも1つのTi含有結晶相であって、
a.ガラスセラミックの結晶相の約2.5〜8質量%、
b.≧約50nmの長さを示す針状の形態、及び
c.ルチル
を含む、Ti含有結晶相;及び、必要に応じて、
(3)スピネル構造を示し、結晶相の1〜10質量%を構成する、1つ以上の結晶相。
(1)15MHzから3.0GHzの周波数範囲で0.03未満の誘電正接によって定められる、無線及びマイクロ波周波数透過性;
(2)0.8MPa・m1/2超の破壊靭性;
(3)約138MPa(20,000psi)超の破壊係数(MOR);
(4)少なくとも400kg/mm2のヌープ硬さ;
(5)4W/m℃未満の熱伝導率;及び
(6)0.1体積%未満の細孔率。
[Al2O3]のモルに対する[Li2O+Na2O+K2O+MgO+ZnO]のモル合計の比は、約0.8から約1.5の範囲内でありうる。
本開示の態様及び/又は実施形態に従ったβ−スポジュメンガラスセラミック;イオン交換可能なβ−スポジュメンガラスセラミック;及び/又はイオン交換したβ−スポジュメンガラスセラミックの色を説明するためのCIELAB色空間座標(例えば、CIE L*;CIE a*;及びCIE b*;又はCIE L*、a*、及びb*;又はL*、a*、及びb*)は、ここに参照することによってその記載が取り込まれる、F. W. Billmeyer, Jr., “Current American Practice in Color Measurement,” Applied Optics, Vol. 8, No. 4, pp. 737-750 (April 1969)に記載されるものなど、全反射(正反射を含む)測定から当該技術分野で知られた方法によって決定された。すなわち、全反射(正反射を含む)測定は、約33mmΦ×0.8mmの厚さを測定する、試料ディスクを使用する光学研磨用に調製された表面で行われた。このような全反射(正反射を含む)測定を行うための器材、及びL*;a*;及びb*の色空間座標を得るための変換結果は、以下を含んでいた:
波長範囲250〜3300nm(例えば、紫外線(UV:300〜400nm)、可視(Vis:400〜700nm)、及び赤外線(IR:700〜2500nm)において全反射(正反射を含む)に対して効力があるように適切に設けられ、かつ構成された、市販のVarian Cary 5G又はPerkinElmer Lambda 950 UV−VIS−NIR分光光度計などの積分球を備えた紫外可視近赤外(UV−VIS−NIR)分光光度計;及び
測定結果をF02光源及び10度の標準観測者に基づいてCIELAB色空間座標(L*;a*;及びb*)に変換するUV−VIS−NIR分光光度計に結合された色測定のための解析ソフトウェア(米国フロリダ州ウエストパームビーチ所在のThermo Scientific社から市販されるGRAMS分光ソフトウェアスイートのUV/VIS/NIRアプリケーションパック)。
a)モル%で、
i)約60から約75の範囲のSiO2、
ii)約10から約18の範囲のAl2O3、
iii)約5から約14の範囲のLi2O、及び
iv)約4.5から約20の範囲のB2O3
を含む組成物、及び
b)少なくとも約245N(約25kgf)のビッカース亀裂開始閾値
を含み、
β−スポジュメンが主結晶相である、ガラスセラミック物品。
ビッカース亀裂開始閾値が少なくとも約294N(約30kgf)である、実施形態1に記載のガラスセラミック物品。
ビッカース亀裂開始閾値が少なくとも約343N(約35kgf)である、実施形態1に記載のガラスセラミック物品。
ビッカース亀裂開始閾値が少なくとも約392N(約40kgf)である、実施形態1に記載のガラスセラミック物品。
ビッカース亀裂開始閾値が少なくとも約441N(約45kgf)である、実施形態1に記載のガラスセラミック物品。
残留ガラス中に存在するB2O3の少なくとも約50%が3配位のホウ素カチオンを含む、実施形態1に記載のガラスセラミック物品。
[Li2O+Na2O+K2O+MgO+ZnO]の合計モル/[Al2O3]のモルの比が約0.8から約1.5の範囲にある、実施形態1に記載のガラスセラミック物品。
前記組成物が、
v)0から約8の範囲のMgO、
vi)0から約4の範囲のZnO、
vii)約2から約5の範囲のTiO2、
viii)0から約5の範囲のNa2O、
ix)0から約4の範囲のK2O、及び
x)約0.05から約0.5の範囲のSnO2
をさらに含む、実施形態1に記載のガラスセラミック物品。
前記組成物が、モル%で、
i)約60から約70の範囲のSiO2、
ii)約10から約16の範囲のAl2O3、
iii)約7から約10の範囲のLi2O、
iv)約6から約8の範囲のB2O3、
v)約2から約5の範囲のMgO、
vi)約1から約2の範囲のZnO、
vii)約3から約4の範囲のTiO2、
viii)約0.4から約0.6の範囲のNa2O、及び
ix)約0.2から約0.5の範囲のSnO2
を含む、実施形態1に記載のガラスセラミック物品。
前記組成物が約6から約10モル%の範囲のB2O3を含む、実施形態1に記載のガラスセラミック物品。
前記組成物が約6から約8モル%の範囲のB2O3を含む、実施形態1に記載のガラスセラミック物品。
前記組成物が0から約3モル%の範囲のZrO2を含む、実施形態1に記載のガラスセラミック物品。
前記ガラスセラミック物品が、10°の観測者角度及びCIE発光F02で、分光光度計を用いた正反射を含めた反射スペクトル測定から決定して、
a)約−2から約1の範囲のCIE a*;
b)約−5から約−2の範囲のCIE b*;及び
c)約80から約98の範囲のCIE L*
を含むCIELAB色空間座標に存在する色を含む、実施形態1に記載のガラスセラミック物品。
イオン交換によって形成された圧縮応力層をさらに備える、実施形態1に記載のガラスセラミック物品。
前記圧縮応力層が、少なくとも80MPaの圧縮応力及び物品の全厚の少なくとも約2%の層深さ(DOL)を有する、実施形態14に記載のガラスセラミック物品。
a)結晶性ガラスを、約1℃/分から約10℃/分の範囲の速度で約700℃から810℃の範囲の核形成温度まで加熱する工程であって、前記結晶性ガラスが、モル%で、
i)約60から約75の範囲のSiO2、
ii)約10から約18の範囲のAl2O3、
iii)約5から約14の範囲のLi2O、及び
iv)約4.5から約20の範囲のB2O3
を含む、工程;
b)前記結晶性ガラスを前記核形成温度に維持して、核形成した結晶性ガラスを生成する工程;
c)前記核形成した結晶性ガラスを、約1℃/分から約10℃/分の範囲の速度で約850℃から1200℃の範囲の結晶化温度まで加熱する工程;及び
d)前記核形成した結晶性ガラスを前記結晶化温度に維持して、主結晶相としてβ−スポジュメンを有するガラスセラミックを生成する工程であって、前記ガラスセラミックが少なくとも約245N(約25kgf)のビッカース亀裂開始閾値を含む、工程
を含む、ガラスセラミックを製造する方法。
前記ガラスセラミックをイオン交換して圧縮応力層を形成する工程をさらに含む、実施形態16に記載の方法。
前記圧縮応力層が、少なくとも80MPaの圧縮応力及びガラスセラミックの全厚の少なくとも約2%の層深さ(DOL)を有する、実施形態17に記載の方法。
残留ガラス中に存在するB2O3の少なくとも約50%が3配位のホウ素カチオンを含む、実施形態16に記載の方法。
前記ビッカース亀裂開始閾値が少なくとも約294N(約30kgf)である、実施形態16に記載の方法。
前記ビッカース亀裂開始閾値が少なくとも約343N(約35kgf)である、実施形態16に記載の方法。
前記ビッカース亀裂開始閾値が少なくとも約392N(約40kgf)である、実施形態16に記載の方法。
前記ビッカース亀裂開始閾値が少なくとも約441N(約45kgf)である、実施形態16に記載の方法。
結晶性ガラス中の[Li2O+Na2O+K2O+MgO+ZnO]の合計モル/[Al2O3]のモルの比が約0.8から約1.5の範囲にある、実施形態16に記載の方法。
工程d)の後に、前記ガラスセラミックをクエンチして冷却する工程をさらに含む、実施形態16に記載の方法。
前記ガラスセラミックが約800℃から約1100℃の範囲の温度になった時点でクエンチする工程を含む、実施形態25に記載の方法。
前記結晶性ガラスが、
v)0から約8の範囲のMgO、
vi)0から約4の範囲のZnO、
vii)約2から約5の範囲のTiO2、
viii)0から約5の範囲のNa2O、
ix)0から約4の範囲のK2O、及び
x)約0.05から約0.5の範囲のSnO2
をさらに含む、実施形態16に記載の方法。
Claims (9)
- a)モル%で、
i)約60から約75の範囲のSiO2、
ii)約10から約18の範囲のAl2O3、
iii)約5から約14の範囲のLi2O、及び
iv)5.8から7.6の範囲のB2O3
を含む組成物から形成されたイオン交換したガラスセラミック物品であって、
b)少なくとも約245N(約25kgf)のビッカース亀裂開始閾値
を含み、
β−スポジュメンが主結晶相である、イオン交換したガラスセラミック物品。 - 前記ビッカース亀裂開始閾値が少なくとも約294N(約30kgf)である、請求項1に記載のイオン交換したガラスセラミック物品。
- 残留ガラス中に存在するB2O3の少なくとも約50%が3配位のホウ素カチオンを含む、請求項1又は2に記載のイオン交換したガラスセラミック物品。
- 前記組成物が、[Li2O+Na2O+K2O+MgO+ZnO]の合計モル/[Al2O3]のモルの比が約0.8から約1.5の範囲にある、請求項1から3のいずれか一項に記載のイオン交換したガラスセラミック物品。
- 前記組成物が、モル%で、
i)約60から約70の範囲のSiO2、
ii)約10から約16の範囲のAl2O3、
iii)約7から約10の範囲のLi2O、
iv)5.8から7.6の範囲のB2O3、
v)約2から約5の範囲のMgO、
vi)約1から約2の範囲のZnO、
vii)約3から約4の範囲のTiO2、
viii)約0.4から約0.6の範囲のNa2O、及び
ix)約0.2から約0.5の範囲のSnO2
を含む、請求項1から4のいずれか一項に記載のイオン交換したガラスセラミック物品。 - a)結晶性ガラスを、約1℃/分から約10℃/分の範囲の速度で約700℃から810℃の範囲の核形成温度まで加熱する工程であって、前記結晶性ガラスが、モル%で、
i)約60から約75の範囲のSiO2、
ii)約10から約18の範囲のAl2O3、
iii)約5から約14の範囲のLi2O、及び
iv)5.8から7.6の範囲のB2O3
を含む、工程;
b)前記結晶性ガラスを前記核形成温度に維持して、核形成した結晶性ガラスを生成する工程;
c)前記核形成した結晶性ガラスを、約1℃/分から約10℃/分の範囲の速度で約850℃から1200℃の範囲の結晶化温度まで加熱する工程;
d)前記核形成した結晶性ガラスを前記結晶化温度に維持して、主結晶相としてβ−スポジュメンを有するガラスセラミックを生成する工程、および
e)前記ガラスセラミックをイオン交換処理に供する工程、
を有してなり、前記イオン交換したガラスセラミックが少なくとも約245N(約25kgf)のビッカース亀裂開始閾値を有する、
イオン交換したガラスセラミックを製造する方法。 - 残留ガラス中に存在するB2O3の少なくとも約50%が3配位のホウ素カチオンを含む、請求項6に記載の方法。
- 前記ビッカース亀裂開始閾値が少なくとも約294N(約30kgf)である、請求項6又は7に記載の方法。
- 工程d)の後、前記ガラスセラミックが約800℃から約1100℃の範囲の温度になった時点で、前記ガラスセラミックをクエンチして冷却する工程をさらに含む、請求項6〜8のいずれか一項に記載の方法。
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EP3160916A1 (en) | 2017-05-03 |
KR102533218B1 (ko) | 2023-05-16 |
JP2017519711A (ja) | 2017-07-20 |
TW201940446A (zh) | 2019-10-16 |
WO2016003960A1 (en) | 2016-01-07 |
US20170327406A1 (en) | 2017-11-16 |
TW201605757A (zh) | 2016-02-16 |
TWI723432B (zh) | 2021-04-01 |
CN106660861A (zh) | 2017-05-10 |
EP3901109A1 (en) | 2021-10-27 |
TWI667215B (zh) | 2019-08-01 |
US10189735B2 (en) | 2019-01-29 |
CN111792848B (zh) | 2023-02-17 |
CN111792848A (zh) | 2020-10-20 |
US20190152834A1 (en) | 2019-05-23 |
KR20170021885A (ko) | 2017-02-28 |
US9751798B2 (en) | 2017-09-05 |
CN106660861B (zh) | 2020-07-31 |
US20150376054A1 (en) | 2015-12-31 |
US10781131B2 (en) | 2020-09-22 |
EP3160916B1 (en) | 2021-08-04 |
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