US20200277220A1 - Uv-transmitting glass and molded products - Google Patents
Uv-transmitting glass and molded products Download PDFInfo
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- US20200277220A1 US20200277220A1 US16/878,674 US202016878674A US2020277220A1 US 20200277220 A1 US20200277220 A1 US 20200277220A1 US 202016878674 A US202016878674 A US 202016878674A US 2020277220 A1 US2020277220 A1 US 2020277220A1
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- US
- United States
- Prior art keywords
- glass
- equal
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- transmitting
- transmitting glass
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 258
- 238000002834 transmittance Methods 0.000 claims abstract description 91
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 59
- 238000002844 melting Methods 0.000 claims description 32
- 230000008018 melting Effects 0.000 claims description 32
- 239000003638 chemical reducing agent Substances 0.000 claims description 28
- 239000012298 atmosphere Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910001887 tin oxide Inorganic materials 0.000 claims description 12
- 238000004435 EPR spectroscopy Methods 0.000 claims description 9
- 239000000156 glass melt Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- 230000002349 favourable effect Effects 0.000 description 26
- 229910052742 iron Inorganic materials 0.000 description 25
- 239000007791 liquid phase Substances 0.000 description 16
- 230000007423 decrease Effects 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 10
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 238000005191 phase separation Methods 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 8
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000004031 devitrification Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- -1 oxide Chemical compound 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 206010040925 Skin striae Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000005303 fluorophosphate glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
-
- 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
- C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
Definitions
- the present disclosure relates to glass having good ultraviolet (UV) transmittance and molded products using the glass.
- UV ultraviolet
- synthetic quartz and sapphire are favorably used because of their good UV transmittance; however, these are high-cost materials when manufacturing products because these are expensive by themselves, require time-consuming processing, and the processing costs are high in order to have desired three-dimensional shapes.
- a high-refractive-index glass having a refractive index of greater than or equal to 1.7 has a low UV transmittance in general; however, according to the present disclosure, it is possible to provide a glass product having a high refractive index while maintaining a good UV transmittance.
- the inventors of the present disclosure have conducted intensive studies in order to solve the above-described problems, and as a result, have found that in a glass made of a multi-component oxide, by lowering the content of the iron component, and by controlling the oxidation state, the light transmittance in the UV region can be improved, and thus, have come to complete the present disclosure.
- a UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance ⁇ 350-400 (%) with respect to light having a wavelength between 350 nm and 400 nm through a 10 mm-thick glass that satisfies the following formula (1):
- another UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance ⁇ 300-350 (%) with respect to light having a wavelength between 300 nm and 350 nm through a 10 mm-thick glass that satisfies the following formula (2):
- yet another UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance ⁇ 260-300 (%) with respect to light having a wavelength between 260 nm and 300 nm through a 10 mm-thick glass that satisfies the following formula (3):
- a molded product according to the present disclosure is made of a UV-transmitting glass according to the present disclosure and has a desired shape.
- FIG. 1 is a graph illustrating a relationship between the added amount of SnO 2 and the external transmittance in Example 2-1;
- FIG. 2 is a graph illustrating a relationship between the added amount of SnO 2 and the external transmittance in Example 2-2.
- UV-transmitting glass according to the present disclosure, and manufacturing methods and molded products of the glass will be described in detail with reference to an embodiment.
- a UV-transmitting glass according to the present disclosure has a good transmittance with respect to light in the UV region, and is useful as the material of a product that transmits UV light.
- a method of manufacturing a UV-transmitting glass according to the present disclosure enables to stably and efficiently manufacture the UV-transmitting glass by simple operations.
- a molded product according to the present disclosure has a good transmittance with respect to light in the UV region and is useful as a product that transmits UV light.
- a UV-transmitting glass of the present embodiment is a glass material made of an oxide, and has a good transmittance of light having a wavelength in the UV region.
- a UV-transmitting glass of the present embodiment for example, a glass that is formed of a multi-component oxide, and has an internal transmittance ⁇ 350-400 (%) with respect to light having a wavelength between 350 nm and 400 nm through a 10 mm-thick glass that satisfies the following formula (1), may be cited.
- a UV-transmitting glass of the present embodiment for example, a glass that is formed of a multi-component oxide, and has an internal transmittance ⁇ 300-350 (%) with respect to light having a wavelength between 300 nm and 350 nm through a 10 mm-thick glass that satisfies the following formula (2), may be cited.
- a UV-transmitting glass of the present embodiment for example, a glass that is formed of a multi-component oxide, and has an internal transmittance ⁇ 260-300 (%) with respect to light having a wavelength between 260 nm and 300 nm through a 10 mm-thick glass that satisfies the following formula (3), may be cited.
- the internal transmittance ⁇ 350-400 is favorably greater than or equal to 93%, more favorably greater than or equal to 95%.
- the internal transmittance ⁇ 300-350 is favorably greater than or equal to 79%, more favorably greater than or equal to 83%, and particularly favorably greater than or equal to 86%.
- the internal transmittance ⁇ 260-300 is favorably greater than or equal to 50%, more favorably greater than or equal to 55%, particularly favorably greater than or equal to 65%, and most favorably greater than or equal to 70%.
- the internal transmittance is a transmittance with respect to a sample manufactured using a UV-transmitting glass to be measured, excluding the surface reflection loss on the incident side and the emission side, which is well known in this technical field, and the measurement may be performed by a commonly practiced method.
- the measurement is performed, for example, as follows.
- a pair of flat samples (a first sample and a second sample) made of glass having the same composition and different thicknesses are prepared. Both sides of each flat sample are made flat, parallel to each other, and optically polished. Denoting the intensity of incident light perpendicularly incident on the optically polished surface of the first sample by Iin(1), and the intensity of outgoing light emitted from the opposite surface by Iout(1), the external transmittance T 1 including the surface reflection loss of the first sample is represented by an intensity ratio Iout(1)/Iin(1).
- the external transmittance T 2 including the surface reflection loss of the second sample is represented by an intensity ratio Iout(2)/Iin(2).
- the internal transmittance ⁇ through a thickness dx (mm) can be calculated by the following formula (a):
- composition of such a UV-transmitting glass is not limited in particular as long as it is a glass made of a multi-component oxide and satisfies the internal transmittances specified as above.
- the glass is made of a multi-component oxide containing multiple species of oxide compounds, and hence, quartz glass is not included.
- composition system of such a UV-transmitting glass specifically, those of glasses having a mother composition of borosilicate glass, silicate glass, phosphate glass, fluorophosphate glass, and the like may be listed.
- the iron component is present in the glass as having the valence of Fe 3+ or Fe 2+ , and the total iron oxide content obtained by converting the iron component contained in the glass into Fe 2 O 3 is represented as T-Fe 2 O 3 (mass ppm).
- T-Fe 2 O 3 is favorably less than or equal to 1.5 mass ppm, more favorably less than or equal to 1 mass ppm, further favorably less than 0.9 mass ppm, and a smaller content is more favorable.
- the above-described iron component is introduced into the glass mainly as impurities contained in the glass raw materials, except for contamination by iron in a dissolution process.
- the iron component it is favorable to reduce the iron component contained in the glass from Fe 3+ to Fe 2+ to adjust the valence.
- the UV transmittance can be improved by reducing the amount of Fe 3+ , which absorbs UV light significantly.
- the method of adjusting the valence of iron as such will be described in detail later, which is possible by adding a component serving as a reducing agent into glass raw materials or glass cullets when melting a glass, by using a non-oxidizing atmosphere when melting the glass, or the like.
- a molded product to be obtained from the glass will have a high Fe 2+ redox.
- the Fe 2+ redox is a ratio of the amount of Fe 2+ to the total iron content, and is obtained as a ratio between the amounts each converted to Fe 2 O 3 .
- the amount of Fe 3+ can also be evaluated by electron spin resonance (ESR); when the amount of Fe 3+ is small, the Fe 3+ intensity measured by ESR is low.
- ESR electron spin resonance
- the type, amount, and dissolution atmosphere of a reducing agent so that the Fe 3+ intensity measured by ESR becomes favorably less than or equal to 0.0215, more favorably less than or equal to 0.0180, even more favorably less than or equal to 0.0150, and particularly favorably less than or equal to 0.0115, it is possible to obtain a glass that exhibits a high transmittance even in a shorter wavelength region.
- the amount of T-Fe 2 O 3 is large, it is favorable to lower the Fe 3+ intensity by increasing the reducibility of the glass.
- the amount of T-Fe 2 O 3 is small, the amount of Fe 3+ is small, and thereby, the Fe 3+ intensity is low.
- the content of Bi 2 O 3 , TiO 2 , WO 3 , and Gd 2 O 3 is favorably less than or equal to 3 mol %, more favorably less than or equal to 1 mol %, and particularly favorably virtually zero, in terms of mol % on an oxide basis.
- the content of Nb 2 O 5 and Ta 2 O 5 is favorably less than or equal to 3 mol %, more favorably less than or equal to 1 mol %, and particularly favorably virtually zero, in terms of mol % on an oxide basis.
- “content being virtually zero” means intentionally excluding the substance, except when unavoidably introduced due to impurities in the glass raw materials, and specifically means a content of less than or equal to 0.01 mol %.
- the following glass composition 1 and glass composition 2 may be listed as favorable ones.
- the glass composition 1 is an example of a composition having a high refractive index n d being greater than or equal to 1.7
- the glass composition 2 is an example of a composition having a low refractive index n d being less than 1.7.
- the present glass composition 1 is a composition containing B 2 O 3 by 10 to 80%, SiO 2 by 0 to 25%, La 2 O 3 by 2 to 32%, and Y 2 O 3 by 0 to 20%, in terms of mol % on an oxide basis.
- B 2 O 3 is an essential component, which can form a glass skeleton, increase the stability of the glass, and increase the UV transmittance.
- mol % is simply abbreviated to % in the glass, it is possible to obtain a stable glass.
- the B 2 O 3 content is favorably greater than or equal to 20%, more favorably greater than or equal to 30%, and particularly favorably greater than or equal to 40%.
- B 2 O 3 content is favorably less than or equal to 75% and more favorably less than or equal to 70%.
- SiO 2 is an optional component that can form a glass skeleton as with B 2 O 3 , increase the stability of the glass, increase the devitrification resistance, and prevent phase separation of the glass.
- SiO 2 content is favorably less than or equal to 20% and more favorably less than or equal to 18%. Note that in order to lower the liquid phase temperature to make the glass less likely to be devitrified, and to improve the chemical durability, it is favorable to contain SiO 2 , and the content thereof is more favorably greater than or equal to 1%, particularly favorably greater than or equal to 3%, and most favorably greater than or equal to 5%.
- La 2 O 3 is an essential component, which can maintain a high UV transmittance while increasing the refractive index.
- a La 2 O 3 content greater than or equal to 2%, it is possible to obtain a desired high refractive index.
- the La 2 O 3 content is favorably greater than or equal to 5%, more favorably greater than or equal to 6%.
- a La 2 O 3 content less than or equal to 32% it is possible to control increase in the liquid phase temperature and to make the glass less likely to be devitrified.
- the La 2 O 3 content is favorably less than or equal to 28%, more favorably less than or equal to 25%, and particularly favorably less than or equal to 22%.
- Y 2 O 3 is a component that can maintain a high UV index while increasing the refractive index, and by coexisting with La 2 O 3 , lower the liquid phase temperature so as to improve the devitrification resistance.
- a Y 2 O 3 content less than or equal to 20%, it is possible to control increase in the melting temperature and the molding temperature, and also to control increase in the liquid phase temperature so as to make the glass less likely to be devitrified.
- the Y 2 O 3 content is favorably less than or equal to 15%, more favorably less than or equal to 13%, and particularly favorably less than or equal to 10%.
- Y 2 O 3 is favorably contained, more favorably by greater than or equal to 2%, particularly favorably by greater than or equal to 4%, and most favorably by greater than or equal to 5%.
- the present glass composition 1 may further contain the following components.
- Li 2 O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component.
- the Li 2 O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- Na 2 O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component.
- the Na 2 O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- K 2 O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component.
- K 2 O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- ZnO is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component that can be contained by a large amount while maintaining the devitrification resistance.
- ZnO content is favorably less than or equal to 33%, more favorably less than or equal to 25%, and particularly favorably less than or equal to 20%.
- MgO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component.
- MgO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- CaO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component.
- the CaO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- SrO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component.
- SrO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- BaO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component.
- the BaO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- ZrO 2 is a component that can increase the refractive index while maintaining a high UV transmittance, and improve the devitrification resistance, which is an optional component.
- ZrO 2 content is favorably less than or equal to 13% and more favorably less than or equal to 10%.
- Al 2 O 3 is a component that can increase the chemical durability, and control phase separation of the glass, which is an optional component.
- Al 2 O 3 content is favorably less than or equal to 5%, more favorably less than or equal to 3%, and particularly favorably less than or equal to 1%.
- Sb 2 O 3 oxidizes the glass; therefore, it is favorable to lower the content in order to increase the deep UV transmittance, which may be less than or equal to 0.1%, favorably less than or equal to 0.05%, more favorably virtually zero.
- the present glass composition 1 in order to reduce the environmental load, it is favorable to contain virtually no PbO and As 2 O 3 except for inevitable contamination. F has volatility; therefore, it is favorable not to contain F in the case of desiring to control fluctuations in striae and optical characteristics.
- the refractive index n d is greater than or equal to 1.7.
- the refractive index n d is favorably greater than or equal to 1.71, more favorably greater than or equal to 1.72, and particularly favorably greater than or equal to 1.73.
- the present glass composition 2 is a composition that contains B 2 O 3 +SiO 2 +P 2 O 5 by 40 to 90%, Li 2 O+Na 2 O+K 2 O by 0 to 30%, MgO+CaO+SrO+BaO by 0 to 20%, in terms of mol % on an oxide basis.
- B 2 O 3 , SiO 2 , and P 2 O 5 are components that form a glass skeleton. If the content of B 2 O 3 +SiO 2 +P 2 O 5 is too large, the solubility decreases; therefore, the content may be less than or equal to 90%, favorably less than or equal to 85%, and more favorably less than or equal to 80%. In order to improve the devitrification resistance, the content may be greater than or equal to 40%, and favorably greater than or equal to 45%. In order to increase the chemical durability, it is favorable to contain SiO 2 , and more favorably by greater than or equal to 5%.
- the SiO 2 content is favorably less than or equal to 70%, more favorably less than or equal to 60%, and particularly favorably less than or equal to 50%.
- it is favorable to contain B 2 O 3 , more favorably by greater than or equal to 5%, and particularly favorably by 10%.
- the B 2 O 3 content is favorably less than or equal to 80%, and more favorably less than or equal to 75%.
- Li 2 O, Na 2 O, and K 2 O may be contained to lower the melting temperature. If the content is too large, the glass tends to be devitrified; therefore, the content of Li 2 O+Na 2 O+K 2 O may be less than or equal to 30%, favorably less than or equal to 25%, and more favorably less than or equal to 20%.
- MgO, CaO, SrO, and BaO may be contained to lower the melting temperature. If the content is too large, the glass tends to be devitrified; therefore, the content of MgO+CaO+SrO+BaO may be less than or equal to 20%, favorably less than or equal to 15%, and more favorably less than or equal to 10%.
- the present glass composition 2 may further contain the following components.
- ZnO is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature.
- the ZnO content may be less than or equal to 10%, and favorably less than or equal to 5%.
- Al 2 O 3 is a component that can increase the chemical durability, and control phase separation of the glass.
- Al 2 O 3 content may be favorably less than or equal to 15%, and more favorably less than or equal to 10%.
- Sb 2 O 3 oxidizes the glass; therefore, it is favorable to lower the content in order to increase the deep UV transmittance, which may be less than or equal to 0.1%, favorably less than or equal to 0.05%, more favorably virtually zero.
- the present glass composition 2 in order to reduce the environmental load, it is favorable to contain virtually no PbO and As 2 O 3 except for inevitable contamination. F has volatility; therefore, it is favorable not to contain F in the case of desiring to control fluctuations in striae and optical characteristics.
- a UV-transmitting glass of the present embodiment favorably has the following characteristics.
- the glass transition temperature Tg is favorably lower than or equal to 650° C., more favorably lower than or equal to 620° C., and particularly favorably lower than or equal to 600° C.
- the present UV-transmitting glass is used in an optical system; therefore, a higher UV transmittance is more favorable.
- a coloration code of ⁇ 70 and ⁇ 5 as an indicator for the external transmittance ⁇ 70 , which represents a wavelength at which a glass having a thickness of 10 mm exhibits 70% of the external transmittance, is favorably less than or equal to 305 nm, more favorably less than or equal to 300 nm, particularly favorably less than or equal to 295 nm, and most favorably less than or equal to 285 nm.
- ⁇ 5 which represents a wavelength at which a glass having a thickness of 10 mm exhibits 5% of the external transmittance, is favorably less than or equal to 240 nm, more favorably less than or equal to 235 nm, particularly favorably less than or equal to 230 nm, and most favorably less than or equal to 220 nm.
- the liquid phase temperature is favorably lower than or equal to 1200° C., more favorably lower than or equal to 1150° C., and further favorably lower than or equal to 1100° C. Note that in the present Description, the liquid phase temperature is a minimum temperature at which a crystal solid is not formed from a glass melt when held at a certain temperature for a certain period of time.
- a method of manufacturing a UV-transmitting glass of the present embodiment is a method of manufacturing a UV-transmitting glass of the above-described embodiment.
- This method of manufacturing a UV-transmitting glass is based on a conventionally known method of manufacturing glass, in which glass raw materials or glass cullets are melted, and the obtained glass melt is cooled and solidified. At this time, in the present embodiment, it is favorable to lower the iron content in the glass and to control the oxidation-reduction state of the components contained in the obtained glass so as to obtain good UV transmission characteristics.
- the glass materials or glass cullets to be prepared are not limited in particular as long as a UV-transmitting glass of the present embodiment can be obtained.
- the raw materials for example, nitrate, sulfate, carbonate, hydroxide, oxide, boric acid, and the like are used. Glass raw materials from which the above-described glass composition 1 or glass composition 2 is obtained are favorable.
- the glass materials or glass cullets are heated to a temperature higher than or equal to the melting temperature to obtain a glass melt; as a melting condition in this process, it is possible to consider two cases for the atmosphere which the glass melt contacts: one is the air atmosphere (an oxidizing atmosphere); and the other is a non-oxidizing atmosphere.
- a method of introducing a non-oxidizing gas such as nitrogen or argon into the furnace, or a method of introducing flame of a burner using a combustible gas that does not contain oxygen, such as city gas, into the furnace, or the like may be used.
- a reducing agent that will remain in the glass to be obtained is considered as a glass raw material, and a reducing agent that will not remain in the glass is considered as an external additive to the glass raw materials.
- a reducing agent used here as those remaining in the glass, SnO 2 , SnO, silicon (Si), aluminum (Al), and fluorides (aluminum fluoride, lanthanum fluoride, etc.); or as those volatilized and not remaining in the glass, carbon (C) and the like may be listed.
- Carbon (C) can be added as a carbohydrate such as carbon powder or sucrose.
- the reducing agent in the case of using a material containing at least one species of tin oxide selected from among SnO 2 and SnO, and in the case where melting is performed in the air atmosphere, it is favorable to add the tin oxide by an amount of more than 0.3 mass % and less than or equal to 3 mass % as the total amount of SnO 2 and SnO. If the content is less than or equal to 0.3 mass %, the effect of improving the UV transmittance is insufficient; therefore, it is favorable to add an amount of greater than or equal to 0.35 mass %. If the content exceeds 3 mass %, the transmittance is lowered on the contrary; therefore, it is added by an amount of favorably less than or equal to 2 mass %, more favorably less than or equal to 1 mass %.
- the tin oxide in the case where melting is performed in a non-oxidizing atmosphere, it is favorable to add the tin oxide by an amount of more than 0 mass % and less than or equal to 0.3 mass % as the total amount of SnO 2 and SnO.
- By adding more than 0 mass % it is possible to further improve the UV transmittance, and it is favorable to add an amount of greater than or equal to 0.01 mass %. If adding the tin oxide by greater than or equal to 0.3 mass %, the transmittance is lowered.
- the amount is favorably less than or equal to 0.2 mass %, and more favorably less than or equal to 0.1 mass %.
- tin oxide is present in a glass as having the valences of Sn 2+ and Sn 4+ , as described above, by determining the amount of tin oxide to be added according to the melting atmosphere, the glass can be stably maintained in a reduced state; therefore, a greater amount of Sn 2+ is detected in the glass-molded product compared with conventional melting methods.
- the amount to be added may be determined according to the glass melting atmosphere and the melting time; for example, in a non-oxidizing atmosphere, it is favorable to externally add the agent by greater than or equal to 0.2 mass % and less than or equal to 1 mass % with respect to 100 mass % of the glass. Note that in this case, as carbon becomes carbon dioxide to be volatilized during the glass manufacturing operations, no carbon component derived from the reducing agent will remain in the UV-transmitting glass to be obtained.
- the molten glass obtained in this way is cooled and solidified by a publicly-known method to obtain a UV-transmitting glass.
- a product having a desired shape can be obtained by performing processing including grinding, polishing, and the like.
- a desired shape is given as it is; therefore, a molded product can be obtained by taking it out of the molding die.
- the obtained glass-molded product may be softened by heating to be pressed against a molding die so as to be shaped.
- a molded product of the present embodiment is a molded object made of a UV-transmitting glass of the present embodiment described above and formed into a desired shape.
- a molded product of the present embodiment can be formed into any shape according to its application, and the molded product may be manufactured by a publicly-known method, for example, a method as described with the method of manufacturing a UV-transmitting glass. Also, in some cases, hot processing such as reheat pressing or redraw processing is performed in a later process.
- Such a molded product can be used without particular limitation as a member that transmits UV light.
- the applications for example, water sterilization devices; curing devices for UV-curable resin; cover glass for UV sensors or the like; sealing materials of UV LEDs (UV light emitting diode); lighting equipment using UV light; optical elements such as lenses and optical filters that require a function of transmitting UV light; materials for photoresist exposure; replacements of optical parts made of quartz or the like such as beam shapers and cut aspheric lenses; core materials used in UV-transmitting optical fibers (the refractive index difference between the core and the clad can be large, and hence, the aperture angle can be widened and the output can be improved); cover glass with lens for laser diodes (LD) and light emitting diodes (LED); lens arrays; and the like may be listed.
- LD laser diodes
- LED light emitting diodes
- the shape of a molded product of the present embodiment may set to be a desired shape according to an application as described above.
- Examples 1-1 to 1-6 are examples according to the embodiment, and Example 1-7 is a comparative example. Also, the glass composition is represented by mass % (or mol %) on an oxide basis.
- Raw materials including nitrate, sulfate, hydroxide, oxide, and boric acid were weighed respectively, mixed thoroughly, and then, placed in a platinum crucible so as to obtain a glass having a composition shown in Table 1, heated and melted in the air at 1300° C. for 3 hours.
- the glass raw materials to be used were selected to have a low content of impurities such as iron and titanium.
- the molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of ⁇ 60° C./h, and a glass 1 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe 3+ intensity of less than or equal to 0.0215.
- Example 1-1 SnO 2 was added as the reducing agent, and the glass raw materials were weighed so as to have a composition shown in Table 1.
- a glass 2 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe 3+ intensity of less than or equal to 0.0215.
- the glass raw materials were weighed so as to have a composition shown in Table 1.
- the raw materials were placed in a platinum crucible, added with 0.4 mass % by outer percent of carbon powder as a reducing agent, and heated at 1300° C. for 3 hours in a melting furnace filled with nitrogen gas, to be melted.
- a glass-molded product was molded by substantially the same molding method as in Example 1-1, and a glass 5 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe 3+ intensity of less than or equal to 0.0215. Note that the added carbon was volatilized as CO 2 when the glass was melted, and hence, did not remain in the glass-molded product.
- the glass raw materials were weighed so as to have a composition shown in Table 1.
- materials having a large iron content were used.
- a glass 7 was obtained.
- the iron content of the glass exceeded 1.5 ppm, and the Fe 3+ intensity exceeded 0.0215 because no reducing agent was added.
- the obtained glass was measured with respect to the refractive index, external transmittance, coloration code, internal transmittance, T-Fe 2 O 3 , and Fe 3+ intensity at a wavelength of 587.56 nm (d-line). Measuring methods of these will be described below.
- the refractive index was measured for a sample processed to have a rectangular parallelepiped shape having a side of greater than or equal to 5 mm and a thickness of greater than or equal to 5 mm, by using a precise refractive index meter (manufactured by Shimadzu Corporation, model: KPR-200, KPR-2000). The refractive index was measured for the sample obtained by being gradually cooled down at a cooling rate of ⁇ 60° C./h.
- the external transmittance was measured for 1 mm-thick and 10 mm-thick samples, each of which was polished on both sides, by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model: U-4100).
- the coloration code was read from the external transmittance at a thickness of 10 mm, which is shown in Table 1 as a wavelength ⁇ 70 at which the external transmittance is 70% and a wavelength ⁇ 5 at which the external transmittance is 5%.
- T 260 an external transmittance at a thickness of 1 mm at a wavelength of 260 nm is shown as T 260 in Table 1.
- the external transmittance was measured for 1 mm-thick and 10 mm-thick samples, and internal transmittances ⁇ at a thickness of 10 mm were obtained by the formulas (a) and (b) described above.
- An internal transmittance ⁇ 350-400 for light having a wavelength of 350 to 400 nm, an internal transmittance ⁇ 300-350 for light having a wavelength of 300 to 350 nm, and an internal transmittance ⁇ 260-300 for light having a wavelength of 260 to 300 nm were obtained, and minimum values in the respective wavelength ranges are shown in Table 1.
- the total iron oxide content (T-Fe 2 O 3 ) was measured by ICP mass spectrometry according to the following procedure. A mixed acid of hydrofluoric acid and sulfuric acid was added to a crushed glass and heated to be decomposed. After the decomposition, hydrochloric acid was added to make the amount constant, and the concentration of Fe was measured by ICP mass spectrometry. The concentration was calculated by a calibration curve prepared using a standard solution. From the measured concentration and the amount of decomposition of the glass, T-Fe 2 O 3 in the glass was calculated. As the ICP mass spectrometer, Agilent 8800 manufactured by Agilent Technologies was used.
- the Fe 3+ intensity was measured by electron spin resonance (ESR) according to the following procedure. 0.3 g of crushed glass was weighed, and a copper nitrate standard solution for ICP was added as an internal standard so as to add Cu 2+ by 30 ⁇ g. After drying the sample at approximately 50° C. for around 2 hours, the sample was filled in a measuring tube for ESR, to measure an electron spin resonance spectrum.
- the device used was an ESR spectrometer manufactured by JEOL Ltd. The ESR measurement conditions are shown in Table 2.
- the Fe 3+ signal intensity and the Cu 2+ signal intensity were defined as in the following formulas, and one obtained by excluding variations in the amplifier magnification and the measured intensity during the measurement was adopted as the Fe 3+ intensity.
- Fe 3+ signal intensity (maximum value of signal intensity of Fe 3+ peak appearing in a magnetic field around 157 mT) ⁇ (minimum value of signal intensity of Fe 3+ peak appearing in the magnetic field around 157 mT)
- Cu 2+ signal intensity (maximum value of signal intensity of Cu 2+ peak appearing in the magnetic field around 310 mT) ⁇ (minimum value of signal intensity of Cu 2+ peak appearing in the magnetic field around 310 mT)
- Fe 3+ intensity (Fe 3+ signal intensity/amplifier magnification when measuring Fe 3+ signal intensity)/(Cu 2+ signal intensity/amplifier magnification when measuring Cu 2+ signal intensity)
- Example 1-1 As shown in Table 1, it can be seen from Example 1-1 that the light transmittance in the UV region can be improved by lowering the iron content. Also, from Examples 1-2 to 1-6, it was understood that when manufacturing a glass, by adding a reducing agent, and/or by setting the atmosphere during melting to be a non-oxidizing atmosphere, the valence of the iron component contained by a tiny amount could be controlled, and further, the light transmittance in the UV region could be improved. Also, although high-refractive-index glass generally has low UV transmittance, as shown with Examples 1-1 to 1-5, glass exhibiting high UV transmittance even having a high refractive index of 1.7 or higher could be realized.
- Example 1-7 in the case of not lowering the iron content and not controlling the valence of the iron component in the glass, it can be seen the transmittance is noticeably lowered. Especially, it can be seen that as the wavelength becomes shorter, the transmittance decreases more strikingly, and it is not possible to obtain a glass with a high UV light transmittance.
- Glass cullets having a composition of SiO 2 by 2.66 mol %, B 2 O 3 by 35.27 mol %, La 2 O 3 by 47.81 mol %, and Y 2 O 3 by 14.25 mol % were placed in a platinum crucible, heated and melted in the air at 1300° C. for 3 hours.
- the molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of ⁇ 60° C./h, and a glass was obtained.
- the glass cullets were prepared to have the added amount of SnO 2 between 0 and 0.5 mass %, and for the obtained glass, a relationship between the added amount of SnO 2 and the external transmittance of the glass at 10-mm thickness at a wavelength of 270 nm was examined; the obtained graph is shown in FIG. 1 .
- Glass cullets having a composition of SiO 2 by 2.66 mol %, B 2 O 3 by 35.27 mol %, La 2 O 3 by 47.81 mol %, and Y 2 O 3 by 14.25 mol % were placed in a platinum crucible, and heated and melted in a melting furnace filled with nitrogen gas at 1300° C. for 3 hours.
- the molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of ⁇ 60° C./h, and a glass was obtained.
- the glass cullets were prepared to have the added amount of SnO 2 between 0 and 0.4 mass %, and for the obtained glass, a relationship between the added amount of SnO 2 and the external transmittance of the glass at 10-mm thickness at a wavelength of 270 nm was examined; the obtained graph is shown in FIG. 2 .
- the external transmittance was measured for a sample having a thickness of 10 mm and polished on both sides, by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model: U-4100). In the measurement, the external transmittance was obtained with respect to light having a wavelength of 270 nm, and plotted results are shown in FIGS. 1 and 2 .
- the transmittance in the UV region is significantly changed depending on the melting atmosphere of the glass and the added amount of the reducing agent.
- the addition of a reducing agent is useful, and the transmittance improves as the added amount increases, but tends to saturate when the added amount of SnO 2 exceeds around 0.35 mass %. Also, according to FIG. 1 , in the melting in the air atmosphere, the addition of a reducing agent is useful, and the transmittance improves as the added amount increases, but tends to saturate when the added amount of SnO 2 exceeds around 0.35 mass %. Also, according to FIG.
- the melting atmosphere and the added amount of the reducing agent have suitable conditions, respectively, and particularly in the non-oxidizing atmosphere, it can be seen that it is favorable to add a tiny amount of a reducing agent. Also, it can be seen that even in the oxidizing atmosphere, the transmittance in the UV region can be greatly improved by adding the reducing agent up to an appropriate amount.
- each of UV-transmitting glasses of the present examples has a good UV transmittance, and the method of manufacturing a UV-transmitting glass of each of the present examples can stably manufacture such a UV-transmitting glass.
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Abstract
Description
- This U.S. non-provisional application is a continuation application of and claims the benefit of priority under 35 U.S.C. § 365(c) from PCT International Application PCT/JP2019/001644 filed on Jan. 21, 2019, which is designated the U.S., and is based upon and claims the benefit of priority of Japanese Patent Application No. 2018-008389 filed on Jan. 22, 2018, the entire contents of which are incorporated herein by reference.
- The present disclosure relates to glass having good ultraviolet (UV) transmittance and molded products using the glass.
- As materials that transmit UV light, synthetic quartz and sapphire are favorably used because of their good UV transmittance; however, these are high-cost materials when manufacturing products because these are expensive by themselves, require time-consuming processing, and the processing costs are high in order to have desired three-dimensional shapes.
- Also, as a glass whose UV transmittance is improved by adjusting the components contained in the glass, examples have been known in which a reducing agent such as an organic substance or metal is added to the glass (see, e.g., Japanese Laid-Open Patent Applications No. 03-93644 and No. 03-93645).
- However, in the case where the melting time during manufacturing becomes longer, a glass as described in these patent documents may be reoxidized by oxygen in the melting atmosphere, which decreases the UV transmittance again.
- Further, it has been known that a high-refractive-index glass having a refractive index of greater than or equal to 1.7 has a low UV transmittance in general; however, according to the present disclosure, it is possible to provide a glass product having a high refractive index while maintaining a good UV transmittance.
- The inventors of the present disclosure have conducted intensive studies in order to solve the above-described problems, and as a result, have found that in a glass made of a multi-component oxide, by lowering the content of the iron component, and by controlling the oxidation state, the light transmittance in the UV region can be improved, and thus, have come to complete the present disclosure.
- According to an aspect in the present disclosure, a UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance τ350-400(%) with respect to light having a wavelength between 350 nm and 400 nm through a 10 mm-thick glass that satisfies the following formula (1):
-
τ350-400≥90 (1). - Also, another UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance τ300-350(%) with respect to light having a wavelength between 300 nm and 350 nm through a 10 mm-thick glass that satisfies the following formula (2):
-
τ300-350≥75 (2). - Also, yet another UV-transmitting glass according to the present disclosure is formed of a multi-component oxide, and has an internal transmittance τ260-300(%) with respect to light having a wavelength between 260 nm and 300 nm through a 10 mm-thick glass that satisfies the following formula (3):
-
τ260-300≥45 (3). - A molded product according to the present disclosure is made of a UV-transmitting glass according to the present disclosure and has a desired shape.
-
FIG. 1 is a graph illustrating a relationship between the added amount of SnO2 and the external transmittance in Example 2-1; and -
FIG. 2 is a graph illustrating a relationship between the added amount of SnO2 and the external transmittance in Example 2-2. - In the following, UV-transmitting glass according to the present disclosure, and manufacturing methods and molded products of the glass will be described in detail with reference to an embodiment.
- A UV-transmitting glass according to the present disclosure has a good transmittance with respect to light in the UV region, and is useful as the material of a product that transmits UV light.
- Further, in the case of having a high refractive index, processability and moldability are sufficient while having optical performance close to that of sapphire, and the production cost of a product can be reduced.
- A method of manufacturing a UV-transmitting glass according to the present disclosure enables to stably and efficiently manufacture the UV-transmitting glass by simple operations.
- A molded product according to the present disclosure has a good transmittance with respect to light in the UV region and is useful as a product that transmits UV light.
- [UV-Transmitting Glass]
- A UV-transmitting glass of the present embodiment is a glass material made of an oxide, and has a good transmittance of light having a wavelength in the UV region.
- As a UV-transmitting glass of the present embodiment, for example, a glass that is formed of a multi-component oxide, and has an internal transmittance τ350-400(%) with respect to light having a wavelength between 350 nm and 400 nm through a 10 mm-thick glass that satisfies the following formula (1), may be cited.
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τ350-400≥90 (1) - Also, as a UV-transmitting glass of the present embodiment, for example, a glass that is formed of a multi-component oxide, and has an internal transmittance τ300-350(%) with respect to light having a wavelength between 300 nm and 350 nm through a 10 mm-thick glass that satisfies the following formula (2), may be cited.
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τ300-350≥75 (2) - Also, as a UV-transmitting glass of the present embodiment, for example, a glass that is formed of a multi-component oxide, and has an internal transmittance τ260-300(%) with respect to light having a wavelength between 260 nm and 300 nm through a 10 mm-thick glass that satisfies the following formula (3), may be cited.
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τ260-300≥45 (3) - In other words, as a UV-transmitting glass of the present embodiment, it is sufficient to satisfy at least one of the characteristics expressed by the above-described formulas (1) to (3), to favorably satisfy two, and to more favorably satisfy all the three. For each of these formulas (1) to (3), it is necessary to satisfy the above-described inequality in the entire wavelength range described above, which may be rephrased that a minimum value of the internal transmittance in each of the above-described wavelength ranges satisfies the corresponding inequality described above.
- Also, in the above-described formulas (1) to (3), it is favorable for the internal transmittances to satisfy the following values. The internal transmittance τ350-400 is favorably greater than or equal to 93%, more favorably greater than or equal to 95%. The internal transmittance τ300-350 is favorably greater than or equal to 79%, more favorably greater than or equal to 83%, and particularly favorably greater than or equal to 86%. The internal transmittance τ260-300 is favorably greater than or equal to 50%, more favorably greater than or equal to 55%, particularly favorably greater than or equal to 65%, and most favorably greater than or equal to 70%.
- In the present Description, the internal transmittance is a transmittance with respect to a sample manufactured using a UV-transmitting glass to be measured, excluding the surface reflection loss on the incident side and the emission side, which is well known in this technical field, and the measurement may be performed by a commonly practiced method. The measurement is performed, for example, as follows.
- A pair of flat samples (a first sample and a second sample) made of glass having the same composition and different thicknesses are prepared. Both sides of each flat sample are made flat, parallel to each other, and optically polished. Denoting the intensity of incident light perpendicularly incident on the optically polished surface of the first sample by Iin(1), and the intensity of outgoing light emitted from the opposite surface by Iout(1), the external transmittance T1 including the surface reflection loss of the first sample is represented by an intensity ratio Iout(1)/Iin(1). Similarly, denoting the intensity of incident light perpendicularly incident on the optically polished surface of the second sample by Iin(2), and the intensity of outgoing light emitted from the opposite surface by Iout(2), the external transmittance T2 including the surface reflection loss of the second sample is represented by an intensity ratio Iout(2)/Iin(2).
- Denoting a thickness of the first sample by d1 (mm) and a thickness of the second sample by d2 (mm) where d1<d2, the internal transmittance τ through a thickness dx (mm) can be calculated by the following formula (a):
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τ=exp[−dx×(ln T1−ln T2)/Δd] (a) - where Δd=d2−d1, and ln means natural logarithm. For a UV-transmitting glass of the present embodiment, an internal transmittance converted to a thickness of 10 mm is defined as an index; therefore, the internal transmittance in the above-described wavelength range is calculated for each wavelength using the following formula (b).
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τ(10 mm)=exp[−10×(ln T1−ln T2)/Δd] (b) - The composition of such a UV-transmitting glass is not limited in particular as long as it is a glass made of a multi-component oxide and satisfies the internal transmittances specified as above. However, the glass is made of a multi-component oxide containing multiple species of oxide compounds, and hence, quartz glass is not included.
- As the composition system of such a UV-transmitting glass, specifically, those of glasses having a mother composition of borosilicate glass, silicate glass, phosphate glass, fluorophosphate glass, and the like may be listed.
- It is favorable that such a glass has a lowered content of the iron component in particular. Here, the iron component is present in the glass as having the valence of Fe3+ or Fe2+, and the total iron oxide content obtained by converting the iron component contained in the glass into Fe2O3 is represented as T-Fe2O3 (mass ppm).
- In a UV-transmitting glass of the present embodiment, T-Fe2O3 is favorably less than or equal to 1.5 mass ppm, more favorably less than or equal to 1 mass ppm, further favorably less than 0.9 mass ppm, and a smaller content is more favorable. The above-described iron component is introduced into the glass mainly as impurities contained in the glass raw materials, except for contamination by iron in a dissolution process.
- Also, regarding the iron component, it is favorable to reduce the iron component contained in the glass from Fe3+ to Fe2+ to adjust the valence. The UV transmittance can be improved by reducing the amount of Fe3+, which absorbs UV light significantly. The method of adjusting the valence of iron as such will be described in detail later, which is possible by adding a component serving as a reducing agent into glass raw materials or glass cullets when melting a glass, by using a non-oxidizing atmosphere when melting the glass, or the like. In this case, a molded product to be obtained from the glass will have a high Fe2+ redox. The Fe2+ redox is a ratio of the amount of Fe2+ to the total iron content, and is obtained as a ratio between the amounts each converted to Fe2O3.
- Also, the amount of Fe3+ can also be evaluated by electron spin resonance (ESR); when the amount of Fe3+ is small, the Fe3+ intensity measured by ESR is low. By selecting the type, amount, and dissolution atmosphere of a reducing agent so that the Fe3+ intensity measured by ESR becomes favorably less than or equal to 0.0215, more favorably less than or equal to 0.0180, even more favorably less than or equal to 0.0150, and particularly favorably less than or equal to 0.0115, it is possible to obtain a glass that exhibits a high transmittance even in a shorter wavelength region. When the amount of T-Fe2O3 is large, it is favorable to lower the Fe3+ intensity by increasing the reducibility of the glass. When the amount of T-Fe2O3 is small, the amount of Fe3+ is small, and thereby, the Fe3+ intensity is low.
- Although it is possible to contain various transition metal oxides as the glass components in general glass, in a UV-transmitting glass according to the present disclosure, in order to improve the UV transmittance, it is favorable to lower the content of a component that absorbs light in the UV region.
- In order to improve the transmittance in the near UV region, in a UV-transmitting glass, for example, the content of Bi2O3, TiO2, WO3, and Gd2O3 is favorably less than or equal to 3 mol %, more favorably less than or equal to 1 mol %, and particularly favorably virtually zero, in terms of mol % on an oxide basis. Also, in order to improve the transmittance in the deep UV region, further, in addition to the above-described restrictions, in a UV-transmitting glass, the content of Nb2O5 and Ta2O5 is favorably less than or equal to 3 mol %, more favorably less than or equal to 1 mol %, and particularly favorably virtually zero, in terms of mol % on an oxide basis.
- Note that in the present Description, “content being virtually zero” means intentionally excluding the substance, except when unavoidably introduced due to impurities in the glass raw materials, and specifically means a content of less than or equal to 0.01 mol %.
- With respect to such a UV-transmitting glass, as more specific glass compositions, for example, the following glass composition 1 and glass composition 2 may be listed as favorable ones. Here, the glass composition 1 is an example of a composition having a high refractive index nd being greater than or equal to 1.7, and the glass composition 2 is an example of a composition having a low refractive index nd being less than 1.7.
- (Glass Composition 1)
- The present glass composition 1 is a composition containing B2O3 by 10 to 80%, SiO2 by 0 to 25%, La2O3 by 2 to 32%, and Y2O3 by 0 to 20%, in terms of mol % on an oxide basis.
- In the present glass composition 1, B2O3 is an essential component, which can form a glass skeleton, increase the stability of the glass, and increase the UV transmittance. By having a B2O3 content greater than or equal to 10 mol % (hereafter, mol % is simply abbreviated to %) in the glass, it is possible to obtain a stable glass. The B2O3 content is favorably greater than or equal to 20%, more favorably greater than or equal to 30%, and particularly favorably greater than or equal to 40%. On the other hand, by having a B2O3 content less than or equal to 80%, it is possible to prevent occurrence of phase separation of the glass. The B2O3 content is favorably less than or equal to 75% and more favorably less than or equal to 70%.
- In the present glass composition 1, SiO2 is an optional component that can form a glass skeleton as with B2O3, increase the stability of the glass, increase the devitrification resistance, and prevent phase separation of the glass. By having an SiO2 content less than or equal to 25%, it is possible to avoid undissolved residue during dissolution. The SiO2 content is favorably less than or equal to 20% and more favorably less than or equal to 18%. Note that in order to lower the liquid phase temperature to make the glass less likely to be devitrified, and to improve the chemical durability, it is favorable to contain SiO2, and the content thereof is more favorably greater than or equal to 1%, particularly favorably greater than or equal to 3%, and most favorably greater than or equal to 5%.
- In the present glass composition 1, La2O3 is an essential component, which can maintain a high UV transmittance while increasing the refractive index. By having a La2O3 content greater than or equal to 2%, it is possible to obtain a desired high refractive index. The La2O3 content is favorably greater than or equal to 5%, more favorably greater than or equal to 6%. On the other hand, by having a La2O3 content less than or equal to 32%, it is possible to control increase in the liquid phase temperature and to make the glass less likely to be devitrified. The La2O3 content is favorably less than or equal to 28%, more favorably less than or equal to 25%, and particularly favorably less than or equal to 22%.
- In the present glass composition 1, Y2O3 is a component that can maintain a high UV index while increasing the refractive index, and by coexisting with La2O3, lower the liquid phase temperature so as to improve the devitrification resistance. By having a Y2O3 content less than or equal to 20%, it is possible to control increase in the melting temperature and the molding temperature, and also to control increase in the liquid phase temperature so as to make the glass less likely to be devitrified. The Y2O3 content is favorably less than or equal to 15%, more favorably less than or equal to 13%, and particularly favorably less than or equal to 10%. In order to increase the refractive index, Y2O3 is favorably contained, more favorably by greater than or equal to 2%, particularly favorably by greater than or equal to 4%, and most favorably by greater than or equal to 5%.
- The present glass composition 1 may further contain the following components.
- In the present glass composition 1, Li2O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component. By having a Li2O content less than or equal to 15%, it is possible to control decrease in the refractive index, and to control increase in the liquid phase temperature. The Li2O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%. In the case of applying hot forming to the glass at a later process, it is necessary to lower the glass transition temperature; in this case, it is favorable to contain Li2O, more favorably by greater than or equal to 1%, and particularly favorably by greater than or equal to 2%.
- In the present glass composition 1, Na2O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component. By having a Na2O content less than or equal to 15%, it is possible to control decrease in the refractive index, and to control increase in the liquid phase temperature. The Na2O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, K2O is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component. By having a K2O content less than or equal to 15%, it is possible to control decrease in the refractive index, and to control increase in the liquid phase temperature. The K2O content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, ZnO is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature, which is an optional component that can be contained by a large amount while maintaining the devitrification resistance. By having a ZnO content less than or equal to 35%, it is possible to control decrease in the refractive index. The ZnO content is favorably less than or equal to 33%, more favorably less than or equal to 25%, and particularly favorably less than or equal to 20%.
- In the present glass composition 1, MgO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component. By having a MgO content less than or equal to 15%, it is possible to control decrease in the refractive index and increase in the liquid phase temperature. The MgO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, CaO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component. By having a CaO content less than or equal to 15%, it is possible to control decrease in the refractive index and increase in the liquid phase temperature. The CaO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, SrO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component. By having an SrO content less than or equal to 15%, it is possible to control decrease in the refractive index and increase in the liquid phase temperature. The SrO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, BaO is a component that can prevent phase separation of the glass, and improve the meltability, which is an optional component. By having a BaO content less than or equal to 15%, it is possible to control decrease in the refractive index and increase in the liquid phase temperature. The BaO content is favorably less than or equal to 13%, more favorably less than or equal to 10%, and particularly favorably less than or equal to 5%.
- In the present glass composition 1, ZrO2 is a component that can increase the refractive index while maintaining a high UV transmittance, and improve the devitrification resistance, which is an optional component. By having a ZrO2 content less than or equal to 15%, it is possible to prevent decrease in the devitrification resistance due to an excessive content. The ZrO2 content is favorably less than or equal to 13% and more favorably less than or equal to 10%.
- In the present glass composition 1, Al2O3 is a component that can increase the chemical durability, and control phase separation of the glass, which is an optional component. By having an Al2O3 content less than or equal to 10%, it is possible to control decrease in the refractive index, and to control increase in the liquid phase temperature. The Al2O3 content is favorably less than or equal to 5%, more favorably less than or equal to 3%, and particularly favorably less than or equal to 1%.
- In the present glass composition 1, Sb2O3 oxidizes the glass; therefore, it is favorable to lower the content in order to increase the deep UV transmittance, which may be less than or equal to 0.1%, favorably less than or equal to 0.05%, more favorably virtually zero.
- In the present glass composition 1, in order to reduce the environmental load, it is favorable to contain virtually no PbO and As2O3 except for inevitable contamination. F has volatility; therefore, it is favorable not to contain F in the case of desiring to control fluctuations in striae and optical characteristics.
- As an optical characteristic of the present glass composition 1, the refractive index nd is greater than or equal to 1.7. Although the suitable refractive index varies depending on applications of molded products, a higher refractive index can make the focal length of a lens shorter, and hence, is suitable for reducing the size and thickness of an optical element. The refractive index nd is favorably greater than or equal to 1.71, more favorably greater than or equal to 1.72, and particularly favorably greater than or equal to 1.73.
- (Glass Composition 2)
- The present glass composition 2 is a composition that contains B2O3+SiO2+P2O5 by 40 to 90%, Li2O+Na2O+K2O by 0 to 30%, MgO+CaO+SrO+BaO by 0 to 20%, in terms of mol % on an oxide basis.
- In the present glass composition 2, B2O3, SiO2, and P2O5 are components that form a glass skeleton. If the content of B2O3+SiO2+P2O5 is too large, the solubility decreases; therefore, the content may be less than or equal to 90%, favorably less than or equal to 85%, and more favorably less than or equal to 80%. In order to improve the devitrification resistance, the content may be greater than or equal to 40%, and favorably greater than or equal to 45%. In order to increase the chemical durability, it is favorable to contain SiO2, and more favorably by greater than or equal to 5%. In order to increase the solubility, the SiO2 content is favorably less than or equal to 70%, more favorably less than or equal to 60%, and particularly favorably less than or equal to 50%. In order to lower the melting temperature, it is favorable to contain B2O3, more favorably by greater than or equal to 5%, and particularly favorably by 10%. In order to prevent phase separation, the B2O3 content is favorably less than or equal to 80%, and more favorably less than or equal to 75%.
- In the present glass composition 2, Li2O, Na2O, and K2O may be contained to lower the melting temperature. If the content is too large, the glass tends to be devitrified; therefore, the content of Li2O+Na2O+K2O may be less than or equal to 30%, favorably less than or equal to 25%, and more favorably less than or equal to 20%.
- In the present glass composition 2, MgO, CaO, SrO, and BaO may be contained to lower the melting temperature. If the content is too large, the glass tends to be devitrified; therefore, the content of MgO+CaO+SrO+BaO may be less than or equal to 20%, favorably less than or equal to 15%, and more favorably less than or equal to 10%.
- The present glass composition 2 may further contain the following components. In the present glass composition 2, ZnO is a component that can improve the meltability of the glass, and lower the glass transition temperature and the softening temperature. The ZnO content may be less than or equal to 10%, and favorably less than or equal to 5%.
- In the present glass composition 2, Al2O3 is a component that can increase the chemical durability, and control phase separation of the glass. By having an Al2O3 content less than or equal to 20%, it is possible to control increase in the liquid phase temperature. The Al2O3 content may be favorably less than or equal to 15%, and more favorably less than or equal to 10%.
- In the present glass composition 2, Sb2O3 oxidizes the glass; therefore, it is favorable to lower the content in order to increase the deep UV transmittance, which may be less than or equal to 0.1%, favorably less than or equal to 0.05%, more favorably virtually zero.
- In the present glass composition 2, in order to reduce the environmental load, it is favorable to contain virtually no PbO and As2O3 except for inevitable contamination. F has volatility; therefore, it is favorable not to contain F in the case of desiring to control fluctuations in striae and optical characteristics.
- Further, a UV-transmitting glass of the present embodiment favorably has the following characteristics.
- In applications that require applying hot forming, such as reheat press molding, to the present UV-transmitting glass, by lowering the glass transition temperature, it is possible to lower the molding temperature during the pressing, and thereby, to improve the durability of a protective film and the like formed on the mold surface. In this case, the glass transition temperature Tg is favorably lower than or equal to 650° C., more favorably lower than or equal to 620° C., and particularly favorably lower than or equal to 600° C.
- The present UV-transmitting glass is used in an optical system; therefore, a higher UV transmittance is more favorable. Using a coloration code of λ70 and λ5 as an indicator for the external transmittance, λ70, which represents a wavelength at which a glass having a thickness of 10 mm exhibits 70% of the external transmittance, is favorably less than or equal to 305 nm, more favorably less than or equal to 300 nm, particularly favorably less than or equal to 295 nm, and most favorably less than or equal to 285 nm. Also, λ5, which represents a wavelength at which a glass having a thickness of 10 mm exhibits 5% of the external transmittance, is favorably less than or equal to 240 nm, more favorably less than or equal to 235 nm, particularly favorably less than or equal to 230 nm, and most favorably less than or equal to 220 nm.
- By lowering the liquid phase temperature, it is possible to make the present UV-transmitting glass less likely to be devitrified when molding a molded product from a glass melt, and to improve the productivity and the glass quality. The liquid phase temperature is favorably lower than or equal to 1200° C., more favorably lower than or equal to 1150° C., and further favorably lower than or equal to 1100° C. Note that in the present Description, the liquid phase temperature is a minimum temperature at which a crystal solid is not formed from a glass melt when held at a certain temperature for a certain period of time.
- [Manufacturing Method of UV-Transmitting Glass]
- A method of manufacturing a UV-transmitting glass of the present embodiment is a method of manufacturing a UV-transmitting glass of the above-described embodiment. This method of manufacturing a UV-transmitting glass is based on a conventionally known method of manufacturing glass, in which glass raw materials or glass cullets are melted, and the obtained glass melt is cooled and solidified. At this time, in the present embodiment, it is favorable to lower the iron content in the glass and to control the oxidation-reduction state of the components contained in the obtained glass so as to obtain good UV transmission characteristics.
- The glass materials or glass cullets to be prepared are not limited in particular as long as a UV-transmitting glass of the present embodiment can be obtained. As the raw materials, for example, nitrate, sulfate, carbonate, hydroxide, oxide, boric acid, and the like are used. Glass raw materials from which the above-described glass composition 1 or glass composition 2 is obtained are favorable.
- The glass materials or glass cullets are heated to a temperature higher than or equal to the melting temperature to obtain a glass melt; as a melting condition in this process, it is possible to consider two cases for the atmosphere which the glass melt contacts: one is the air atmosphere (an oxidizing atmosphere); and the other is a non-oxidizing atmosphere. To prepare a non-oxidizing atmosphere, a method of introducing a non-oxidizing gas such as nitrogen or argon into the furnace, or a method of introducing flame of a burner using a combustible gas that does not contain oxygen, such as city gas, into the furnace, or the like may be used.
- When containing a reducing agent in the glass raw materials or glass cullets, a reducing agent that will remain in the glass to be obtained is considered as a glass raw material, and a reducing agent that will not remain in the glass is considered as an external additive to the glass raw materials. As the reducing agent used here, as those remaining in the glass, SnO2, SnO, silicon (Si), aluminum (Al), and fluorides (aluminum fluoride, lanthanum fluoride, etc.); or as those volatilized and not remaining in the glass, carbon (C) and the like may be listed. Carbon (C) can be added as a carbohydrate such as carbon powder or sucrose.
- Here, as the reducing agent, in the case of using a material containing at least one species of tin oxide selected from among SnO2 and SnO, and in the case where melting is performed in the air atmosphere, it is favorable to add the tin oxide by an amount of more than 0.3 mass % and less than or equal to 3 mass % as the total amount of SnO2 and SnO. If the content is less than or equal to 0.3 mass %, the effect of improving the UV transmittance is insufficient; therefore, it is favorable to add an amount of greater than or equal to 0.35 mass %. If the content exceeds 3 mass %, the transmittance is lowered on the contrary; therefore, it is added by an amount of favorably less than or equal to 2 mass %, more favorably less than or equal to 1 mass %.
- On the other hand, in the case where melting is performed in a non-oxidizing atmosphere, it is favorable to add the tin oxide by an amount of more than 0 mass % and less than or equal to 0.3 mass % as the total amount of SnO2 and SnO. By adding more than 0 mass %, it is possible to further improve the UV transmittance, and it is favorable to add an amount of greater than or equal to 0.01 mass %. If adding the tin oxide by greater than or equal to 0.3 mass %, the transmittance is lowered. The amount is favorably less than or equal to 0.2 mass %, and more favorably less than or equal to 0.1 mass %. Although tin oxide is present in a glass as having the valences of Sn2+ and Sn4+, as described above, by determining the amount of tin oxide to be added according to the melting atmosphere, the glass can be stably maintained in a reduced state; therefore, a greater amount of Sn2+ is detected in the glass-molded product compared with conventional melting methods.
- In the case of using carbon (C) as the reducing agent, the amount to be added may be determined according to the glass melting atmosphere and the melting time; for example, in a non-oxidizing atmosphere, it is favorable to externally add the agent by greater than or equal to 0.2 mass % and less than or equal to 1 mass % with respect to 100 mass % of the glass. Note that in this case, as carbon becomes carbon dioxide to be volatilized during the glass manufacturing operations, no carbon component derived from the reducing agent will remain in the UV-transmitting glass to be obtained.
- The molten glass obtained in this way is cooled and solidified by a publicly-known method to obtain a UV-transmitting glass. In the case of obtaining the UV-transmitting glass as a glass block, a product having a desired shape can be obtained by performing processing including grinding, polishing, and the like. Also, in the case where the molten glass is poured into a molding die or the like to be cooled and solidified, a desired shape is given as it is; therefore, a molded product can be obtained by taking it out of the molding die. At a later process, the obtained glass-molded product may be softened by heating to be pressed against a molding die so as to be shaped.
- [Molded Products]
- A molded product of the present embodiment is a molded object made of a UV-transmitting glass of the present embodiment described above and formed into a desired shape. Here, a molded product of the present embodiment can be formed into any shape according to its application, and the molded product may be manufactured by a publicly-known method, for example, a method as described with the method of manufacturing a UV-transmitting glass. Also, in some cases, hot processing such as reheat pressing or redraw processing is performed in a later process.
- Such a molded product can be used without particular limitation as a member that transmits UV light. As the applications, for example, water sterilization devices; curing devices for UV-curable resin; cover glass for UV sensors or the like; sealing materials of UV LEDs (UV light emitting diode); lighting equipment using UV light; optical elements such as lenses and optical filters that require a function of transmitting UV light; materials for photoresist exposure; replacements of optical parts made of quartz or the like such as beam shapers and cut aspheric lenses; core materials used in UV-transmitting optical fibers (the refractive index difference between the core and the clad can be large, and hence, the aperture angle can be widened and the output can be improved); cover glass with lens for laser diodes (LD) and light emitting diodes (LED); lens arrays; and the like may be listed.
- The shape of a molded product of the present embodiment may set to be a desired shape according to an application as described above.
- In the following, the present disclosure will be described with examples according to the embodiment, but the present disclosure is not limited to these. Examples 1-1 to 1-6 are examples according to the embodiment, and Example 1-7 is a comparative example. Also, the glass composition is represented by mass % (or mol %) on an oxide basis.
- Raw materials including nitrate, sulfate, hydroxide, oxide, and boric acid were weighed respectively, mixed thoroughly, and then, placed in a platinum crucible so as to obtain a glass having a composition shown in Table 1, heated and melted in the air at 1300° C. for 3 hours. The glass raw materials to be used were selected to have a low content of impurities such as iron and titanium.
- The molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of −60° C./h, and a glass 1 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215.
- SnO2 was added as the reducing agent, and the glass raw materials were weighed so as to have a composition shown in Table 1. By substantially the same dissolution method and molding method as in Example 1-1, a glass 2 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215.
- SnO2 was added as the reducing agent, and the glass raw materials were weighed so as to have a composition shown in Table 1. The raw materials were placed in a platinum crucible, and heated at 1300° C. for 3 hours in a melting furnace filled with nitrogen gas, to be melted. Then, a glass-molded product was molded by substantially the same molding method as in Example 1-1, and a glass 3 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215.
- SnO was added as the reducing agent, and the glass raw materials were weighed so as to have a composition shown in Table 1. The raw materials were placed in a platinum crucible, and heated at 1300° C. for 3 hours in a melting furnace filled with nitrogen gas, to be melted. Then, a glass-molded product was molded by substantially the same molding method as in Example 1-1, and a glass 4 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215.
- The glass raw materials were weighed so as to have a composition shown in Table 1. The raw materials were placed in a platinum crucible, added with 0.4 mass % by outer percent of carbon powder as a reducing agent, and heated at 1300° C. for 3 hours in a melting furnace filled with nitrogen gas, to be melted. Then, a glass-molded product was molded by substantially the same molding method as in Example 1-1, and a glass 5 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215. Note that the added carbon was volatilized as CO2 when the glass was melted, and hence, did not remain in the glass-molded product.
- SnO2 was added as the reducing agent, and the glass raw materials were weighed so as to have a composition shown in Table 1. The raw materials were placed in a platinum crucible, and heated at 1300° C. for 3 hours in a melting furnace filled with nitrogen gas, to be melted. Then, a glass-molded product was molded by substantially the same molding method as in Example 1-1, and a glass 6 was obtained that has an iron content of less than or equal to 1.5 mass ppm and an Fe3+ intensity of less than or equal to 0.0215.
- The glass raw materials were weighed so as to have a composition shown in Table 1. As the used glass raw materials, materials having a large iron content were used. By substantially the same dissolution method and molding method as in Example 1-1, a glass 7 was obtained. By using the glass raw materials having a large iron content, the iron content of the glass exceeded 1.5 ppm, and the Fe3+ intensity exceeded 0.0215 because no reducing agent was added.
- [Characteristics]
- The obtained glass was measured with respect to the refractive index, external transmittance, coloration code, internal transmittance, T-Fe2O3, and Fe3+ intensity at a wavelength of 587.56 nm (d-line). Measuring methods of these will be described below.
- (Refractive Index)
- The refractive index was measured for a sample processed to have a rectangular parallelepiped shape having a side of greater than or equal to 5 mm and a thickness of greater than or equal to 5 mm, by using a precise refractive index meter (manufactured by Shimadzu Corporation, model: KPR-200, KPR-2000). The refractive index was measured for the sample obtained by being gradually cooled down at a cooling rate of −60° C./h.
- (External Transmittance and Coloration Code)
- The external transmittance was measured for 1 mm-thick and 10 mm-thick samples, each of which was polished on both sides, by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model: U-4100). The coloration code was read from the external transmittance at a thickness of 10 mm, which is shown in Table 1 as a wavelength λ70 at which the external transmittance is 70% and a wavelength λ5 at which the external transmittance is 5%. Also, an external transmittance at a thickness of 1 mm at a wavelength of 260 nm is shown as T260 in Table 1.
- (Internal Transmittance)
- Regarding the internal transmittance, the external transmittance was measured for 1 mm-thick and 10 mm-thick samples, and internal transmittances τ at a thickness of 10 mm were obtained by the formulas (a) and (b) described above. An internal transmittance τ350-400 for light having a wavelength of 350 to 400 nm, an internal transmittance τ300-350 for light having a wavelength of 300 to 350 nm, and an internal transmittance τ260-300 for light having a wavelength of 260 to 300 nm were obtained, and minimum values in the respective wavelength ranges are shown in Table 1.
- (T-Fe2O3)
- The total iron oxide content (T-Fe2O3) was measured by ICP mass spectrometry according to the following procedure. A mixed acid of hydrofluoric acid and sulfuric acid was added to a crushed glass and heated to be decomposed. After the decomposition, hydrochloric acid was added to make the amount constant, and the concentration of Fe was measured by ICP mass spectrometry. The concentration was calculated by a calibration curve prepared using a standard solution. From the measured concentration and the amount of decomposition of the glass, T-Fe2O3 in the glass was calculated. As the ICP mass spectrometer, Agilent 8800 manufactured by Agilent Technologies was used.
- (Fe3+ Intensity)
- The Fe3+ intensity was measured by electron spin resonance (ESR) according to the following procedure. 0.3 g of crushed glass was weighed, and a copper nitrate standard solution for ICP was added as an internal standard so as to add Cu2+ by 30 μg. After drying the sample at approximately 50° C. for around 2 hours, the sample was filled in a measuring tube for ESR, to measure an electron spin resonance spectrum. The device used was an ESR spectrometer manufactured by JEOL Ltd. The ESR measurement conditions are shown in Table 2.
- In the ESR measured under the conditions shown in Table 2, the Fe3+ signal intensity and the Cu2+ signal intensity were defined as in the following formulas, and one obtained by excluding variations in the amplifier magnification and the measured intensity during the measurement was adopted as the Fe3+ intensity.
-
Fe3+ signal intensity=(maximum value of signal intensity of Fe3+ peak appearing in a magnetic field around 157 mT)−(minimum value of signal intensity of Fe3+ peak appearing in the magnetic field around 157 mT) -
Cu2+ signal intensity=(maximum value of signal intensity of Cu2+ peak appearing in the magnetic field around 310 mT)−(minimum value of signal intensity of Cu2+ peak appearing in the magnetic field around 310 mT) -
Fe3+ intensity=(Fe3+ signal intensity/amplifier magnification when measuring Fe3+ signal intensity)/(Cu2+ signal intensity/amplifier magnification when measuring Cu2+ signal intensity) -
TABLE 1 Ex. 1-1 Ex. 1-2 Ex. 1-3 Ex. 1-4 Ex. 1-5 Ex. 1-6 Ex. 1-7 Composition SiO2 2.66 [5.83] 2.65 [5.80] 2.66 [5.82] 2.66 [5.82] 2.66 [5.83] 5.47 [5.61] 2.66 [5.83] (Mess % B2O3 35.27 [66.59] 35.1 [66.30] 35.26 [66.58] 35.26 [66.57] 35.27 [66.59] 83.06 [73.44] 35.27 [66.59] [mol %]) La2O3 47.81 [19.29] 47.58 [19.21] 47.80 [19.28] 47.79 [19.82] 47.81 [19,29] — 47.81 [19.29] Y2O3 14.25 [8.26] 14.18 [8.26] 14.25 [8.29] 14.24 [8.29] 14.25 [8.29] — 14.25 [8.29] Li2O — — — — — 6.54 [13.47] — MgO — — — — — 4.9 [7.48] — SnO2 — 0.5 [0.43] 0.03 [0.03] — — 0.03 [0.01] — SnO — — — 0.04 [0.04] — — — Total 100 [100] 100 [100] 100 [100] 100 [100] 100 [100] 100 [100] 100 [100] N2 atmosphere Solubility N2 N2 Carbon added N2 condition Air Air atmosphere atmosphe by 0.4 mass % atmosphere Air Char- Minimum internal τ 350-400 94 96 97 98 96 95 86 acteristics transmittance with τ 300-350 81 85 90 91 90 85 46 thickness of 10 mm % τ 250-300 53 58 72 72 74 75 19 Degree of λ 70 303 290 275 273 278 249 344 pigmentation (nm) λ 5 233 227 215 211 211 <210 243 External transmittance T260 (%) 77.5 77.7 82.5 81.4 82.0 87.5 71.4 Refractive index nd 1.74 1.74 1.74 1.74 1.74 1.53 1.74 T-Fe2O3 (mass ppm) 0.84 0.78 0.81 0.88 0.71 0.80 1.87 Fe3+ intensity 0.0112 0.0090 0.0059 0.0026 0.0055 0.0055 0.0329 -
TABLE 2 Fe Cu Freq 9.436 9.436 GHz Power 4 4 mW C.Field 330 330 mT SwWid(±) 250 250 mT SwTime 2 2 min ModWid 0.63 0.63 mT Amp 500 20 TimeC 0.1 0.1 sec - As shown in Table 1, it can be seen from Example 1-1 that the light transmittance in the UV region can be improved by lowering the iron content. Also, from Examples 1-2 to 1-6, it was understood that when manufacturing a glass, by adding a reducing agent, and/or by setting the atmosphere during melting to be a non-oxidizing atmosphere, the valence of the iron component contained by a tiny amount could be controlled, and further, the light transmittance in the UV region could be improved. Also, although high-refractive-index glass generally has low UV transmittance, as shown with Examples 1-1 to 1-5, glass exhibiting high UV transmittance even having a high refractive index of 1.7 or higher could be realized. On the other hand, as shown with Example 1-7, in the case of not lowering the iron content and not controlling the valence of the iron component in the glass, it can be seen the transmittance is noticeably lowered. Especially, it can be seen that as the wavelength becomes shorter, the transmittance decreases more strikingly, and it is not possible to obtain a glass with a high UV light transmittance.
- Glass cullets having a composition of SiO2 by 2.66 mol %, B2O3 by 35.27 mol %, La2O3 by 47.81 mol %, and Y2O3 by 14.25 mol % were placed in a platinum crucible, heated and melted in the air at 1300° C. for 3 hours.
- The molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of −60° C./h, and a glass was obtained. At this time, the glass cullets were prepared to have the added amount of SnO2 between 0 and 0.5 mass %, and for the obtained glass, a relationship between the added amount of SnO2 and the external transmittance of the glass at 10-mm thickness at a wavelength of 270 nm was examined; the obtained graph is shown in
FIG. 1 . - Glass cullets having a composition of SiO2 by 2.66 mol %, B2O3 by 35.27 mol %, La2O3 by 47.81 mol %, and Y2O3 by 14.25 mol % were placed in a platinum crucible, and heated and melted in a melting furnace filled with nitrogen gas at 1300° C. for 3 hours.
- The molten glass was poured into a preheated mold to be cooled and formed to be a plate, held at a temperature near the glass transition temperature for 4 hours, and then, gradually cooled down to room temperature at a cooling rate of −60° C./h, and a glass was obtained. At this time, the glass cullets were prepared to have the added amount of SnO2 between 0 and 0.4 mass %, and for the obtained glass, a relationship between the added amount of SnO2 and the external transmittance of the glass at 10-mm thickness at a wavelength of 270 nm was examined; the obtained graph is shown in
FIG. 2 . - (External Transmittance)
- The external transmittance was measured for a sample having a thickness of 10 mm and polished on both sides, by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, model: U-4100). In the measurement, the external transmittance was obtained with respect to light having a wavelength of 270 nm, and plotted results are shown in
FIGS. 1 and 2 . - As illustrated in
FIGS. 1 and 2 , in Examples 2-1 and 2-2, it can be understood that the transmittance in the UV region is significantly changed depending on the melting atmosphere of the glass and the added amount of the reducing agent. According toFIG. 1 , in the melting in the air atmosphere, the addition of a reducing agent is useful, and the transmittance improves as the added amount increases, but tends to saturate when the added amount of SnO2 exceeds around 0.35 mass %. Also, according toFIG. 2 , in the melting in a non-oxidizing atmosphere, the transmittance is greatly improved by adding a tiny amount of SnO2, but once exceeding the optimal amount of SnO2 that improves the transmittance most, the transmittance decreases as the added amount of SnO2 increases. In Examples 2-1 and 2-2, although SnO2 was added, similar results are obtained when SnO or a mixture of SnO and SnO2 are added. - In other words, the melting atmosphere and the added amount of the reducing agent have suitable conditions, respectively, and particularly in the non-oxidizing atmosphere, it can be seen that it is favorable to add a tiny amount of a reducing agent. Also, it can be seen that even in the oxidizing atmosphere, the transmittance in the UV region can be greatly improved by adding the reducing agent up to an appropriate amount.
- As above, it was found that each of UV-transmitting glasses of the present examples has a good UV transmittance, and the method of manufacturing a UV-transmitting glass of each of the present examples can stably manufacture such a UV-transmitting glass.
- The present disclosure has been described in detail with reference to specific embodiments, and it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present inventive concept.
Claims (16)
τ350-400≥90 (1).
τ300-350≥75 (2).
τ260-300≥45 (3).
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