TWI557085B - 具有高含量的經氧化之鐵的含鋰玻璃及其製備方法 - Google Patents
具有高含量的經氧化之鐵的含鋰玻璃及其製備方法 Download PDFInfo
- Publication number
- TWI557085B TWI557085B TW102106453A TW102106453A TWI557085B TW I557085 B TWI557085 B TW I557085B TW 102106453 A TW102106453 A TW 102106453A TW 102106453 A TW102106453 A TW 102106453A TW I557085 B TWI557085 B TW I557085B
- Authority
- TW
- Taiwan
- Prior art keywords
- glass
- range
- weight
- feo
- lithium
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims description 122
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 88
- 229910052742 iron Inorganic materials 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 15
- 229910052744 lithium Inorganic materials 0.000 title description 15
- 239000006123 lithium glass Substances 0.000 claims description 97
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 84
- 239000000203 mixture Substances 0.000 claims description 58
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 38
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 37
- 239000007800 oxidant agent Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- 239000006060 molten glass Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 20
- 239000006066 glass batch Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 12
- 238000002834 transmittance Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000002985 plastic film Substances 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011229 interlayer Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 239000005345 chemically strengthened glass Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 82
- 101000842368 Homo sapiens Protein HIRA Proteins 0.000 description 32
- 102100030473 Protein HIRA Human genes 0.000 description 32
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 27
- 238000007670 refining Methods 0.000 description 13
- 230000004297 night vision Effects 0.000 description 12
- 238000007496 glass forming Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000005329 float glass Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000038 blue colorant Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- IISIZTZBVOYMAH-UHFFFAOYSA-K calcium;sodium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Na+].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O IISIZTZBVOYMAH-UHFFFAOYSA-K 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- DEPUMLCRMAUJIS-UHFFFAOYSA-N dicalcium;disodium;dioxido(oxo)silane Chemical compound [Na+].[Na+].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DEPUMLCRMAUJIS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000006099 infrared radiation absorber Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
- B32B17/10045—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10064—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising at least two glass sheets, only one of which being an outer layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10082—Properties of the bulk of a glass sheet
- B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10128—Treatment of at least one glass sheet
- B32B17/10137—Chemical strengthening
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/173—Apparatus for changing the composition of the molten glass in glass furnaces, e.g. for colouring the molten glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
-
- 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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0407—Transparent bullet-proof laminatesinformative reference: layered products essentially comprising glass in general B32B17/06, e.g. B32B17/10009; manufacture or composition of glass, e.g. joining glass to glass C03; permanent multiple-glazing windows, e.g. with spacing therebetween, E06B3/66
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B13/00—Optical objectives specially designed for the purposes specified below
- G02B13/14—Optical objectives specially designed for the purposes specified below for use with infrared or ultraviolet radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/18—Aircraft
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2204/00—Glasses, glazes or enamels with special properties
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C4/00—Compositions for glass with special properties
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- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
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Description
本發明係關於一種具有高含量的經氧化之鐵之玻璃,及關於該等玻璃之製法,及更特定言之,係關於一種自製造高紅外吸收玻璃(亦即,具有高含量之經還原的鐵之玻璃)之運轉期轉變為製造低紅外吸收玻璃(亦即,具有低含量之經還原的鐵之玻璃)之運轉期之方法,及藉此製得之玻璃。本文中亦揭示一種自製造低紅外吸收玻璃(亦即,具有低含量之經還原的鐵之玻璃)之運轉期轉變為製造高紅外吸收玻璃(亦即,具有高含量之經還原的鐵之玻璃)之運轉期之方法,及藉此製得之玻璃。如本文所用之術語「運轉期」意指使用預定量之玻璃批料或成分來製造預定量的玻璃,例如(但不限於)具有預定特性範圍(例如(但不限於)光學及彩色特性)之扁平玻璃帶。
以下論述中所特別關注者為含鋰玻璃之製法。如熟習本技藝者所明瞭,含鋰玻璃通常被用作製造經離子交換強化之玻璃的基板。含鋰玻璃之一種類型揭示於美國專利案第4,156,755號(「後文中亦稱之為「USPN '755」」),該專利案以引用的方式併入本文中。
一般而言,鐵並非製造離子交換法用之含鋰玻璃之必需成分,然而,通常有少量的鐵以玻璃批料成分中之雜質存於含鋰玻璃中,或鐵係經添加至該等玻璃批料中,以提供具有期望特性(例如(但不限於)
光學及/或彩色特性)之含鋰玻璃。市售玻璃中呈Fe2O3之總鐵氧化物含量取決於產品要求,然通常在50-1200份/1百萬份{後文中亦稱為「PPM」}或0.005-0.12%總鐵(以氧化物基礎之重量計)(後文中稱為「重量百分比」或「重量%」)範圍內,此等被認為是透明玻璃組合物。更特定言之,可以亞鐵離子(FeO)或鐵離子(Fe2O3)形式進行鐵之添加。於熔化該等玻璃批料期間,於鐵之正鐵形式(Fe+++)與鐵之亞鐵形式(Fe++)之間達成平衡,其中約25-30重量%之鐵係呈亞鐵形式(Fe++)及70-75重量%之鐵係呈正鐵形式(Fe+++)。氧化鐵Fe2O3為強紫外輻射吸收劑及其於玻璃中作為黃色著色劑,及氧化亞鐵FeO為強紅外輻射吸收劑及其於玻璃中作為藍色著色劑。本論述中所特別關注者為氧化亞鐵FeO。
於玻璃片材(例如(但不限於)論述之含鋰玻璃片材,後文中亦稱為「鋰玻璃片材」)例如(但不限於)論述地欲在彎曲及成型之前進行加熱時之實例中,該鋰玻璃片材之組合物通常包括在0.02至0.04重量%範圍內之氧化亞鐵(FeO),且該鋰玻璃片材具有0.2至0.4之氧化還原比(更詳細地論述於下文)。於含鋰玻璃(後文中亦稱為「鋰玻璃」)在本發明實施中欲作為觀測窗口用於紅外設備(例如(但不限於)紅外夜視鏡)、或作為透明盔甲或航空窗口之組件時之實例中,氧化亞鐵較佳在0.001至0.010重量%範圍內,且該鋰玻璃具有在0.005至0.10範圍內之較佳氧化還原比。就欲經加熱來增加紅外波長之吸收以減少鋰玻璃片材達到彎曲溫度之加熱時間之鋰玻璃片材而言,氧化亞鐵的重量%更高。就依據本發明教示欲用於紅外設備之觀測窗口來增加透過該觀測窗口之紅外能透射率%之鋰玻璃而言,氧化亞鐵的重量%低。
伴隨自製造高紅外吸收(後文中亦稱為「HIRA」)鋰玻璃之運轉期至製造本發明之低紅外吸收(後文中亦稱為「LIRA」)鋰玻璃之運轉期、及/或自製造本發明之LIRA鋰玻璃之運轉期至製造HIRA鋰玻璃之
運轉期之其中一缺點為在自一運轉期結束時(例如,製造HIRA鋰玻璃之運轉期結束時)開始及在下一運轉期開始時(例如,製造LIRA鋰玻璃之運轉期開始時)結束之期間所製得之符合針對LIRA鋰玻璃或HIRA鋰玻璃之規格之玻璃量。不符合作為LIRA鋰玻璃及HIRA鋰玻璃使用之規格之玻璃通常係經報廢或作為碎玻璃使用。熟習本技藝者現可明瞭將在自一運轉期轉變至另一運轉期期間所製得之玻璃棄置係昂貴的,此因鋰玻璃之相當高的批料成本及浪費在製造不可用玻璃或邊緣品質玻璃上之時間之故。
因此,宜提供一種最小化或消除與自製造可用HIRA鋰玻璃或可用LIRA鋰玻璃之運轉期分別轉變成製造可用LIRA鋰玻璃或可用HIRA鋰玻璃之運轉期相關聯之缺點之方法。
本發明之一非限制性實施例係關於一種玻璃組合物,其尤其包含:
及選自在大於0至0.50重量%範圍內之氧化鈰、在大於0至0.75重量%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
本發明之另一非限制性實施例係關於一種用於觀測輻射紅外能之裝置,該裝置包括具有至少一條通道之外殼,該通道具有第一開口端及第二開口端、安裝在該通道中用於觀測輻射紅外能之透鏡系統,其改善處包括:
鄰近該通道之一端安裝的化學強化彈道玻璃透鏡,該彈道玻璃透鏡包括第一表面、相對之第二表面及在該彈道玻璃透鏡之該等第一及第二表面之間之玻璃段,該玻璃段尤其包含:
及選自在大於0至0.50重量%範圍內之氧化鈰、在大於0至0.75重量%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
此外,本發明之另一非限制性實施例係關於一種在爐中將熔融玻璃自具有在0.02至0.04重量%範圍內之FeO及在0.2至0.4範圍內之氧
化還原比之熔融高紅外吸收鋰玻璃組合物轉變成具有在0.0005至0.015重量%範圍內之FeO、在0.005至0.15範圍內之氧化還原比及可氧化該FeO之預定量之第一氧化劑之熔融低紅外吸收鋰玻璃組合物之方法,該方法尤其包括:饋入玻璃批料物質,其具有可提供具有在0.0005至0.015重量%範圍內之FeO、在0.005至0.15範圍內之氧化還原比及可氧化該FeO之預定量之第一氧化劑之熔融低紅外吸收鋰玻璃組合物之成分;將第二氧化劑添加至該玻璃批料物質,其量等於在爐中氧化該熔融玻璃中之FeO達預定時間段之該第一氧化劑的量之一或兩倍,及在該預定時間段之後停止以上步驟之實施。
再者,本發明之一非限制性實施例係關於一種包括複數層玻璃片材(其中該等玻璃片材之至少一者係經化學強化)及視需要之塑膠片材之層壓透明玻璃(例如,飛機及陸上車輛擋風玻璃),其中該等玻璃片材及該等塑膠片材係藉由塑膠間層層壓在一起,且該等玻璃片材之至少一者具有尤其包含以下組份之玻璃組合物:
及選自在大於0至0.50 wt%範圍內之氧化鈰、在大於0至0.75重量
%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
此外,本發明係關於一種在爐中將熔融玻璃自具有在0.0005至0.015重量%範圍內之FeO及在0.005至0.10範圍內之氧化還原比之熔融低紅外吸收鋰玻璃組合物轉變成具有在0.02至0.04重量%範圍內之FeO及在0.2至0.4範圍內之氧化還原比之高紅外吸收鋰玻璃組合物之方法,其尤其係藉由以下步驟實施:饋入玻璃批料物質,其具有可提供熔融高紅外吸收鋰玻璃組合物及可增加該FeO之預定量之第一還原劑之成分;將第二還原劑添加至該玻璃批料物質,其量等於在爐中增加該熔融玻璃中之FeO達預定時間段之該第一還原劑的量之一或兩倍,及在該預定時間段之後停止前述步驟之實施。
20‧‧‧精煉爐/爐
22‧‧‧底部
24‧‧‧頂部
26‧‧‧側壁/熔融段
28‧‧‧HIRA或LIRA鋰玻璃批料物質/批料物質
30‧‧‧進口
32‧‧‧爐20之延伸部
34‧‧‧毯覆物
36‧‧‧熔融玻璃38之表面
38‧‧‧熔融玻璃
39‧‧‧玻璃形成室40之進入端
40‧‧‧玻璃形成室
42‧‧‧燃燒器口
43‧‧‧噴嘴
46‧‧‧進料端壁/熔融段
48‧‧‧熔融段
54‧‧‧腰部
56‧‧‧精煉段
70‧‧‧夜視步槍瞄準鏡
72‧‧‧管
74‧‧‧夜視放大透鏡系統
76‧‧‧通道
78‧‧‧彈道透鏡
84‧‧‧窗口
86‧‧‧LIRA鋰化學強化玻璃片材
88‧‧‧塑膠片材
90‧‧‧塑膠間層材料
圖1A及1B為與依據本發明教示用以製造浮法玻璃帶之該類型玻璃形成室連接之玻璃熔融爐的橫截面平面視圖。
圖2為顯示於圖1A中之該玻璃熔融室之立面橫截面側視圖。
圖3為顯示由藉由不同量CeO2及MnO2氧化FeO所產生之氧化還原值及近似亞鐵態鐵(FeO)含量之圖。
圖4為顯示藉由不同量CeO2及MnO2氧化亞鐵態鐵(FeO)之圖。
圖5為具有依據本發明教示所製得之保護透鏡之本發明夜視器之橫截面側視圖。
圖6為併有本發明特徵之層壓彈道透鏡或窗口之立面側視圖。
如本文所用,空間或方向性術語諸如「內部」、「外部」、「左側」、「右側」、「向上」、「向下」、「水平」、「垂直」、及類似者係如其於圖繪製中所顯示者與本發明相關聯。然而,應明瞭本發明可採取多種不同定位,因此,該等術語不被認為係限制性的。
此外,用於本說明書及申請專利範圍中之所有表示尺寸、物理特性等等之數值在所有實例中均應理解為由術語「約」修飾。因此,除非有相反指示,否則描述於以下說明書及申請專利範圍中之數值可根據期望及/或企圖藉由本發明獲得的性質而改變。至少而非作為一種嘗試來限制均等論於申請專利範圍之範疇的應用,各數值參數至少應根據所報導有效位數的數目及藉由應用尋常捨入技術來解釋。此外,本文所揭示之所有範圍應理解為涵蓋包含於其中之任何及所有子範圍。例如,所述範圍「1至10」應被視為包括介於(含)最小值1與(含)最大值10之間之任何及所有子範圍;亦即,所有以最小值1或更大開始及以最大值10或更小結束之子範圍,例如,1至6.7、或3.2至8.1、或5.5至10。再者,如本文所用,術語「安裝於...之上」意指安裝於其上但不一定需與其表面接觸。例如,一物件或一物件之組件「安裝於」另一物件或一物件之組件「之上」分別不排除有材料存在於該等物件之間,或存在於該物件之組件之間。
在論述本發明之若干非限制性實施例之前,應明瞭本發明之應用並不限於本文中所顯示及所論述特定非限制性實施例之細節,因為本發明可包括其他實施例。此外,本文中用以論述本發明之術語係基於闡述之目的而不具限制性。再者,除非另外指出,否則以下論述中類似參考數字指示同類元件。
本發明之非限制性實施例係使用揭示於USPN‘755中之鋰玻璃組合物來揭示,然而,本發明並不侷限於此,及可實施本發明以自一製造具有高經氧化鐵之含量(例如(但不限於)在0.02至0.04重量%範圍內之氧化亞鐵)及在0.2至0.4範圍內之氧化還原比之鈉鈣矽酸鹽玻璃之運轉期轉變為另一製造具有低經氧化鐵之含量(例如(但不限於)在0.001至0.010重量%範圍內之氧化亞鐵)及在0.005至0.15範圍內之氧化還原比之鈉鈣矽酸鹽玻璃之運轉期。
如目前所可明瞭,可添加Fe2O3及/或FeO作為著色劑或性質調節劑。存在於本文所揭示鋰玻璃中之鐵的總量係根據標準分析實務以Fe2O3表示,但其不表示所有鐵係實際地呈Fe2O3形式。同樣地,呈亞鐵態之鐵的量係以FeO報告,儘管其實際上可能並非以FeO存在於玻璃中。為了反映本文所揭示玻璃組合物中之亞鐵及正鐵態鐵的相對量,術語「氧化還原比」將意指以FeO表示之呈亞鐵態之鐵的量除以以Fe2O3表示之總鐵的量。此外,除非另有陳述,否則本說明書中之術語「總鐵」將意指以Fe2O3表示之總鐵及術語「FeO」將意指以FeO表示之呈亞鐵態之鐵。
揭示於USPN‘755中之含鋰玻璃之材料或成分範圍列於下表1中。
利用X-射線螢光光譜法(亦稱為「XRFS」)來測定玻璃中除鋰外之所有氧化物之重量百分比。藉由原子吸收測定玻璃中之氧化鋰的重量百分比。
可包含少量(總計至多約5重量%)之其他玻璃形成原料及玻璃調節劑或著色劑,例如MgO、MnO、TiO2、Sb2O3、As2O3、K2O、PbO、ZnO及CaO,及其混合物。如熟習本技藝者所明瞭,Sb2O3及
As2O3為用於玻璃片材拉製法之氧化劑,但其不相容於浮法玻璃製程,因為浮法玻璃室之還原條件會將Sb2O3及As2O3分別還原為銻及砷金屬。
於本發明之一非限制性實施例中,當例如但不限於論述地在彎曲及/或成型該片材之前欲加熱具有表1組合物之鋰玻璃片材時,鋰玻璃組合物包含表1之成分加上在0.02至0.05重量%範圍內,及較佳在0.03至0.038重量%範圍內之氧化亞鐵,及其氧化還原比在0.2至0.4範圍內及較佳在0.2至0.35範圍內(後文中前述玻璃亦稱為「高紅外吸收鋰玻璃」或「HIRA鋰玻璃」)。於製造HIRA鋰玻璃之運轉期期間,將硫酸鹽及碳添加至玻璃批料成分。該等硫酸鹽及碳添加可增加氧化亞鐵含量,以維持熔融玻璃於期望的氧化還原比範圍中。
於本發明之另一非限制性實施例中,當將具有表1組合物之含鋰玻璃用作紅外設備(例如(但不限於)紅外夜視鏡、夜視器(例如步槍瞄準鏡))之觀測窗口時,該鋰玻璃組合物包含表1之成分。如所示,鐵之氧化物未作為組份列出,然而,如熟習本技藝者所明瞭,預期鐵之氧化物(例如亞鐵態鐵)將呈於批料物質中所見的雜質(例如碎玻璃)存在於玻璃中。在可存在亞鐵態鐵之程度上,本發明涵蓋本發明之玻璃將包含表1之組合物加上在0.0005至0.015重量%範圍內,及較佳在0.001至0.010重量%範圍內之氧化亞鐵,及其氧化還原比在0.005至0.15及較佳0.005至0.10範圍內(後文中,前述玻璃亦稱為「低紅外吸收含鋰玻璃」或「LIRA鋰玻璃」)。預期總鐵(Fe2O3)將在50至200 ppm Fe2O3範圍內。於製造LIRA鋰玻璃之運轉期中,將與所選玻璃製程相容之氧化劑添加至玻璃,例如,將氧化鈰、氧化錳、氧化銻、氧化砷及其組合添加至玻璃批料成分,以將熔融玻璃維持在LIRA鋰玻璃之氧化還原比範圍中。
如上所論述,氧化亞鐵之重量%對HIRA鋰玻璃而言較高,以增
加紅外波長之吸收而減少玻璃達到彎曲溫度之加熱時間或提供太陽熱控制水平,及亞鐵態鐵之重量%對LIRA鋰玻璃而言較低,以減少紅外觀測範圍內紅外能之吸收及增加紅外觀測範圍內紅外能之透射率%以增進對紅外產生物體之觀測。為清楚起見,紫外光波長範圍為電磁頻譜之300至380奈米(後文中亦稱為「nm」);可見光波長範圍為380至780 nm;及近紅外光波長範圍為800至2100 nm。該紅外觀測波長範圍係與裝置相關。於本發明之一非限制性實施例中,該紅外觀測波長範圍為電磁頻譜之400至920 nm。於本發明之實務中,該LIRA鋰玻璃較佳具有等於及大於88%之可見光透射率、更佳大於89%之可見光透射率及最佳大於90%之可見光透射率;等於及大於80%之紅外光透射率、更佳大於85%之紅外光透射率及最佳等於及大於90%之紅外光透射率;及等於及大於80%之紅外觀測透射率、更佳大於85%之紅外觀測透射率及最佳大於90%之紅外觀測透射率。
此外,於本發明之實務中,該HIRA鋰玻璃具有小於88%之可見光透射率;小於75%之紅外光透射率;小於80%之紅外觀測透射率。
以上所給出之該LIRA鋰玻璃之光譜性質係於0.223英寸(5.7毫米)之厚度下報告。可見光透射率係使用CIE標準照明體A以2°觀測者於380至780奈米之波長範圍內測得。紅外光透射率係使用Parry Moon air mass 2.0直接太陽輻射數據在800至2100 nm之波長範圍內測得。觀測透射率係使用CIE標準照明體A之相對光譜照射及觀測裝置之響應函數於400至930 nm之波長範圍內測得。
本發明之該等LIRA及HIRA鋰玻璃之製造可使用習知之非真空精煉浮法玻璃系統,例如(但不限於)圖1及2中所顯示之類型,或使用真空精煉浮法玻璃系統,例如(但不限於)揭示於美國專利案編號4,792,536及5,030,594中之類型,該等專利案以引用的方式併入本文中)。
參照圖1A、1B及2,習知之連續饋料、橫向槽燃燒、玻璃熔融及非真空精煉爐20包括由耐火材料製成之底部22、頂部24及側壁26形成之封閉體。該等HIRA或LIRA鋰玻璃批料物質28係以任何方便或常用方式通過爐20之延伸部32(稱為填充進料)中之進口30(參見圖2)引入,以形成浮在熔融玻璃38之表面36上之毯覆物34(參見圖2)。如圖1A及1B中所顯示之玻璃之總體進展係於該等圖中自左側至右側,朝向在本技藝中用以製造浮法扁平玻璃之類型之玻璃形成室40之進入端39(參見圖1B)。
用以熔化該等批料物質28及加熱該熔融玻璃38之火焰(未顯示)自沿著該等側壁26隔開之燃燒器口42發出(參見圖2)及經導向及橫跨該熔融玻璃38之該表面36。如熟習本技藝者所知曉,於前半個加熱循環期間,火焰自該槽20之一側上該等口各者中之噴嘴43(參見圖2)發出,同時該爐之排氣移動通過該爐之相對側上之該等口。於後半個加熱循環期間,該等口之功能逆轉,該等排氣口為燃燒口,及該等燃燒口為排氣口。顯示於圖1A、1B及2中之類型之爐之燃燒循環為技藝中所熟知及認為無需進一步論述。
如熟習本技藝者所可明瞭,本發明涵蓋使用空氣與燃料氣體之混合物、或氧氣與燃料氣體之混合物,以產生火焰來加熱該等批料物質及熔融玻璃。關於在玻璃熔爐中使用氧氣及燃料氣體之論述,可參考美國專利申請公開案第2009-0205711 A1號,標題為「利用光伏打元件回收廢熱(Use of Photovoltaic for Waste Heat Recovery)」,該公開案以引用的方式併入本文中。
自批料饋料端或進料端壁46順流移動之該等玻璃批料物質28在該爐20之熔融段48中熔化,及該熔融玻璃38移動通過腰部54(參見圖1B)到達該爐20之精煉段56。於該精煉段56中,移除該熔融玻璃38中之氣泡,及該熔融玻璃38在該熔融玻璃通過該精煉段56時經混合或均
質化。該熔融玻璃38係以任何方便或常用方式自該精煉段56遞送至包括於該玻璃形成室40中之熔融金屬池(未顯示)上。在所遞送之熔融玻璃38移動通過位於該熔融金屬池(未顯示)上之該玻璃形成室40時,該熔融玻璃經定尺寸及冷卻。尺寸穩定的經定尺寸玻璃帶(未顯示)自該玻璃形成室40移入退火窯(未顯示)中。顯示於圖1A、1B及2中之類型、及論述於上文之類型之玻璃製造設備為相關技藝所熟知及據認為無需進一步論述。
如熟習本技藝者現可明瞭,當自製造HIRA鋰玻璃之運轉期轉變為製造LIRA鋰玻璃之運轉期時,在製造HIRA鋰玻璃之運轉期結束時該爐20(參見圖1A、1B及2)中所裝納之熔融HIRA鋰玻璃中之亞鐵態鐵較佳減低至0.0005至0.015重量%之範圍,及更佳減低至0.001-0.010重量%之範圍,及氧化還原比較佳減低至0.005-0.15之範圍及更佳減低至0.005-0.10之範圍。於本發明之實務中,爐中熔融HIRA鋰玻璃(例如1850噸)之轉化至熔融LIRA鋰玻璃係在3至4天內完成,而在不存在氧化劑下僅藉由添加LIRA鋰玻璃批料成分來進行轉化將耗時約2週。
於本發明之實務中,可使用氧化劑在3至4天內達成自熔融HIRA鋰玻璃至熔融LIRA鋰玻璃之轉變。於本發明之一非限制性實施例中,使用氧化鈰(CeO2)及/或氧化錳(MnO2)來將亞鐵態鐵氧化為正鐵態鐵,因為如上所論述,其等可與顯示於圖1A、1B及2中之玻璃製程相容。於本發明之較佳實務中,使用氧化鈰(CeO2)來將亞鐵態鐵氧化.為正鐵態鐵,因為如所進行之實驗顯示,氧化鈰(CeO2)係比氧化錳(MnO2)更有效的氧化劑。
更特定言之,製得顯示於表2中之玻璃之樣本(亦稱為「對照樣本」);添加CeO2之顯示於表1中之玻璃之樣本(亦稱為「鈰樣本」)及添加MnO2之顯示於表1中之玻璃之樣本(亦稱為「錳樣本」)。樣本1-5為具有不同量氧化鈰之鈰樣本,及樣本6及7為具有不同量氧化錳之錳
樣本。
圖3為顯示氧化還原比及近似FeO含量之圖,及圖4為顯示對照組樣本及樣本1-7之氧化亞鐵含量(於縱座標(y軸)上)及氧化鈰及氧化錳之重量%(於橫座標(x軸)上)之圖。對照組樣本數據點係在y軸上。於本發明之較佳實務中,使用氧化鈰來將亞鐵態鐵氧化至正鐵態鐵,因為如圖3及4所顯示,氧化鈰係比氧化錳更有效的氧化劑,及氧化鈰可使玻璃「脫色」。更特定言之,氧化鈰並非玻璃中之著色劑,但氧化鈰為玻璃中之強效氧化劑,及其於脫色玻璃中之功能係將亞鐵態鐵(Fe++)氧化為正鐵(Fe+++)態鐵。雖然氧化鈰適用於將殘留的微量亞鐵態鐵脫色,但使用氧化鈰具限制性,例如但不限於論述地,將LIRA鋰玻璃暴露至太陽對該玻璃具有過度曝光效應,此起因於Ce+++至Ce++++之光氧化及Fe+++至Fe++之光還原。如熟習本技藝者所明瞭,鈰之過度曝光效應及Fe+++至Fe++之光還原減低透射率,及增加該玻璃於電磁頻譜之可見光及IR範圍內之吸收。因為可見光及紅外光透射率之減低小於1%,故氧化鈰較佳係氧化亞鐵態鐵。然而,本發明涵蓋添加氧化錳替代氧化鈰及添加氧化錳及氧化鈰之混合物。
於本發明之實務中,可使用在大於0至0.50重量%範圍內之氧化
鈰;較佳在0.02至0.45重量%之範圍內,及最佳在0.04至0.40重量%之範圍內。氧化鈰之其他範圍包括(但不限於)0.01至0.15重量%;0.02至0.10重量%及0.03至0.07重量%。可使用在大於0至0.75重量%範圍內之氧化錳,較佳在0.02至0.50重量%範圍內,及最佳地,其含量為0.04至0.45重量%。如可明瞭,於本發明之實務中,可使用CeO2與MnO2之混合物來氧化亞鐵態鐵。一般而言,對於給定範圍之MnO2,一份CeO2可替代1.10至1.50份MnO2,及對於給定範圍之CeO2,1.10至1.5份MnO2可替代一份CeO2。具較低總鐵含量之玻璃可使用較少量的氧化鈰或氧化錳。在本說明書中,氧化鈰或氧化錳之量將分別意指以CeO2或MnO2表示之總鈰或錳,儘管該等組份實際上可能並非以CeO2或MnO2存在於玻璃中。
於本發明之以下非限制性實施例中,運轉期A之作用係製造HIRA鋰玻璃。運轉期A經指示結束及運轉期B開始製造LIRA鋰玻璃。經製得之HIRA鋰玻璃之組成及欲製得之LIRA鋰玻璃之組成顯示於表3中。
在進行運轉期A期間,將該等HIRA鋰玻璃批料物質饋入該爐20(參見圖1A、1B及2)中,熔融,精煉,及使經精煉之玻璃移入如上所論述之該玻璃形成室40中,以製得具有顯示於表3中之組成之HIRA鋰玻璃。在運轉期A欲結束之指定時間,將LIRA鋰玻璃之玻璃批料物質移入如上所論述之該爐20之該熔融段48以啟動運轉期B。於運轉期B之前36小時期間,LIRA鋰玻璃之批料物質係經調配以提供具有在0.04-0.90重量%範圍內之氧化鈰(亦即,針對表3鋰玻璃所指示氧化鈰量的兩倍)的鋰玻璃。在36小時期間後,LIRA鋰玻璃之批料物質係經調配以提供具有在0.02-0.45 wt%範圍內之氧化鈰的鋰玻璃(參見表
3)。
於本發明之一實施例中,將碳酸鈰添加至該等批料物質,以於玻璃中提供氧化鈰。為製得表3之LIRA鋰玻璃,將在0.033-0.75重量%範圍內之碳酸鈰添加至該等批料物質。對於初始LIRA鋰玻璃批料物質(運轉期B之前36小時期間),將在0.066-1.50重量%範圍內之碳酸鈰添加至該等批料物質。於運轉期B之最初36小時期間結束時,將碳酸鈰減低至0.033-0.75重量%之範圍,以進行運轉期B來製造表3之LIRA鋰玻璃。在運轉期B之前36小時期間內的額外碳酸鈰係要氧化該熔融段26及該爐20之該精煉段56中之亞鐵態鐵。於最初36小時期間結束時,使LIRA鋰玻璃之玻璃批料物質移入如上所論述之該爐20之該熔融段46中。
於本發明之另一非限制性實施例中,如製造的玻璃具有足量的UV吸收劑(例如氧化鈰),則在36小時脈衝後,不需要另外添加碳酸鈰,假設使用具有小於0.0005重量%之足夠低的鐵批料(例如,但不限於,本發明批料)來製造不具有UV吸收劑之玻璃。
本發明不受限於脈衝數目或長度、或該等脈衝期間氧化鈰之重量%。於本發明之實務中,脈衝期間氧化鈰之重量%通常為LIRA鋰玻璃批料中氧化鈰之重量%的2至3倍,及脈衝數目通常為一或二。可視需要改變各脈衝的時段。關於在自運轉期A轉變為運轉期B時使用CeO2來氧化亞鐵態鐵之上述程序適用於使用MnO2、或CeO2與MnO2之混合物來自製造HIRA鋰玻璃之運轉期A轉變為製造LIRA鋰玻璃之運轉期B之本發明實務。雖然程序相同,但因氧化鈰係比氧化錳更有效的氧化劑,故MnO2、及CeO2與MnO2之混合物之重量%增加。
本發明不限於將例如(但不限於)CeO2、MnO2、及CeO2與MnO2之混合物之氧化劑添加至該等批料物質,及本發明涵蓋將額外氧化劑添加至含於該精煉段56中之熔融玻璃或含於在該腰部54上游位置的該熔
融器36中之熔融玻璃。
於本發明之另一非限制性實施例中,藉由添加還原劑將正鐵態鐵還原為亞鐵態鐵,使製造LIRA鋰玻璃之運轉期轉變為製造HIRA鋰玻璃之運轉期。可用於本發明實務之還原劑包括(但不限於)碳、例如(但不限於)石墨之含碳材料、蔗糖(C12H22O11)、煤、矽金屬及氧化錫(SnO2)。本發明之其他非限制性實施例包括(但不限於)改變用於製造不同類型鈉鈣矽酸鹽玻璃或任何其他類型玻璃之運轉期,例如,自HIRA或LIRA鋰玻璃變為鈉鈣矽酸鹽玻璃,或反之亦然。
於運轉期A及B期間製得的本發明HIRA鋰玻璃及LIRA鋰玻璃之用途不限於本發明,及可經處理用於陸上、空中、太空、水上及水下交通工具之窗戶;用於商業及住宅窗戶之透明玻璃,用於太陽能收集器之蓋,及用於彈道觀測窗口。該HIRA鋰玻璃一般係用於使用提供可見光之光源之觀測窗口,及一般不被推薦用於觀測來自物體之紅外能,例如,不推薦將HIRA鋰玻璃用於夜視鏡。就夜視設備而言,推薦用該LIRA鋰玻璃來保護該夜視設備(例如(但不限於)夜視鏡及夜視器)之透鏡系統。更特定言之及參照圖5,其顯示具有管72及安裝在該管72之通道76中之夜視放大透鏡系統74之夜視步槍瞄準鏡70。由化學強化LIRA鋰玻璃製成之彈道透鏡78安裝在與該透鏡系統74隔開之管的末端處。利用該配置,藉由本發明之該等化學強化LIRA鋰玻璃透鏡保護該透鏡系統74以防破損。LIRA鋰玻璃亦可用於特殊應用,包括(但不限於)本發明之用於傢俱、器具、及淋浴門。
參照圖6,其顯示彈道透鏡或窗口84之一非限制性實施例。該窗口84包括藉由用於層壓技藝中之類型之塑膠間層材料90層壓在一起之複數層LIRA鋰化學強化玻璃片材86及塑膠片材88。
於本發明非限制性實施例之實務中,該等LIRA及HIRA鋰玻璃可係未經塗覆或塗覆有任何類型之塗層,例如(但不限於)選擇性地通過
預定波長範圍之光及能量之環境塗層、光催化膜或減水薄膜、或(例如)揭示於美國專利案編號5,873,203及5,469,657中之類型之透明導電性氧化物,該等專利案以引用的方式併入本文中。
本發明不受限於以上所提出及所論述之該等本發明實施例,其等僅僅係為了達成說明之目的而提出,及本發明之範疇僅受限於以下申請專利範圍及任何在本申請案中具有直接或間接行數地新增至申請案之其他請求項之範疇。
20‧‧‧精煉爐/爐
26‧‧‧側壁/熔融段
28‧‧‧HIRA或LIRA鋰玻璃批料物質
32‧‧‧爐20之延伸部
34‧‧‧毯覆物
36‧‧‧熔融玻璃38之表面
38‧‧‧熔融玻璃
39‧‧‧玻璃形成室40之進入端
40‧‧‧玻璃形成室
42‧‧‧燃燒器口
46‧‧‧進料端壁/熔融段
48‧‧‧熔融段
54‧‧‧腰部
56‧‧‧精煉段
Claims (23)
- 一種玻璃組合物,其包含:組份 範圍SiO2 60-63重量% Na2O 10-12重量% Li2O 4-5.5重量% Al2O3 17-19重量% ZrO2 3.5-5重量% (Al2O3+ZrO2) 21.5-24重量% FeO 0.0005-0.015重量% Fe2O3(總鐵) 50-1200 ppm;及選自在大於0至0.50重量%範圍內之氧化鈰、在大於0至0.75重量%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
- 如請求項1之玻璃組合物,其中氧化鈰係在0.01至0.15重量%範圍內。
- 如請求項1之玻璃組合物,其中該FeO係在0.001-0.010重量%範圍內。
- 如請求項1之玻璃組合物,其中該Fe2O3(總鐵)係在50至200 ppm範圍內。
- 如請求項1之玻璃組合物,其中該氧化還原比係在0.005至0.10範圍內。
- 如請求項1之玻璃組合物,其中該氧化劑係選自在0.02至0.45重量%範圍內之氧化鈰、在0.02至0.50重量%範圍內之氧化錳及其混合物之群。
- 如請求項1之玻璃組合物,其中該FeO係在0.001-0.010重量%範圍內;該總鐵係在50至200 ppm範圍內;該氧化還原比係在0.005至0.10範圍內及該氧化劑係選自在0.02至0.45重量%範圍內之氧化鈰、在0.02至0.50重量%範圍內之氧化錳及其混合物之群。
- 一種用於觀測輻射紅外能之裝置,該裝置包括具有至少一條通道之外殼,該通道具有第一開口端及第二開口端,及一用於觀測輻射紅外能之透鏡系統,其改良處包括:鄰近該通道之一端安裝之化學強化彈道玻璃透鏡,該彈道玻璃透鏡包括第一表面、相對之第二表面及在該彈道玻璃透鏡之該等第一及第二表面之間之玻璃段,該玻璃段包含: 及選自在大於0至0.50重量%範圍內之氧化鈰、在大於0至0.75重量%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
- 如請求項8之裝置,其中該透鏡具有大於88%之可見光透射率、大於80%之紅外光透射率、及大於80%之紅外觀測透射率,該等透射率係針對具有0.223英寸(5.7毫米)厚度之玻璃透鏡。
- 如請求項8之裝置,其中該玻璃段之FeO係在0.001-0.010重量%範 圍內。
- 如請求項10之裝置,其中該玻璃段之氧化還原比係在0.005至0.10範圍內。
- 如請求項8之裝置,其中該氧化劑係選自在0.02至0.45重量%範圍內之氧化鈰、在0.02至0.50重量%範圍內之氧化錳及其混合物之群。
- 一種在爐中使熔融玻璃自具有在0.02至0.04重量%範圍內之FeO及在0.2至0.4範圍內之氧化還原比之熔融高紅外吸收鋰玻璃組合物轉變成具有在0.0005至0.015重量%範圍內之FeO、在0.005至0.10範圍內之氧化還原比及可氧化該FeO之預定量之第一氧化劑之熔融低紅外吸收鋰玻璃組合物之方法,該方法包括:饋入玻璃批料物質,其具有可提供具有在0.0005至0.015重量%範圍內之FeO、在0.005至0.10範圍內之氧化還原比及可氧化該FeO之預定量之第一氧化劑之熔融低紅外吸收鋰玻璃組合物之成分;將第二氧化劑添加至該玻璃批料物質,其量等於在爐中氧化熔融玻璃中之該FeO達預定時間段之該第一氧化劑的量之一或兩倍,及在該預定時間段之後停止前述步驟之實施。
- 如請求項13之方法,其中該等第一及第二氧化劑係選自CeO2及MnO2及其混合物之群。
- 如請求項14之方法,其中該等第一及第二氧化劑各為CeO2。
- 如請求項14之方法,其中該等第一及第二氧化劑各為MnO2。
- 一種依據請求項13之方法製得之玻璃,該玻璃係自具有在0.001至0.010重量%範圍內之FeO、在0.005至0.10範圍內之氧化還原比及預定量之第一氧化劑之熔融低紅外吸收鋰玻璃組合物製得。
- 一種層壓透明玻璃,其包括藉由塑膠間層層壓在一起之複數層化學強化玻璃片材及視情況之塑膠片材,其中該等玻璃片材之至少一者具有包含以下組份之玻璃組合物: 及選自在大於0至0.50重量%範圍內之氧化鈰、在大於0至0.75重量%範圍內之氧化錳及其混合物之群之氧化劑,及在0.005-0.15範圍內之氧化還原比。
- 如請求項18之層壓透明玻璃,其中該層壓透明玻璃係選自飛機窗戶及陸上、空中、太空、水上及水下交通工具窗戶之群。
- 如請求項18之層壓透明玻璃,其中該窗戶為擋風玻璃。
- 如請求項18之層壓透明玻璃,其中,於該玻璃組合物中,該FeO係在0.001-0.010重量%範圍內;該總鐵係在50至200 ppm範圍內;該氧化還原比係在0.005至0.10範圍內及該氧化劑係選自在0.02至0.45重量%範圍內之氧化鈰、在0.02至0.50重量%範圍內之氧化錳及其混合物之群。
- 一種在爐中使熔融玻璃自具有在0.0005至0.015重量%範圍內之FeO及在0.005至0.10範圍內之氧化還原比之熔融低紅外吸收鋰玻璃組合物轉變成具有在0.02至0.04重量%範圍內之FeO及在0.2至 0.4範圍內之氧化還原比之高紅外吸收鋰玻璃組合物之方法,該方法包括:饋入玻璃批料物質,其具有可提供該熔融高紅外吸收鋰玻璃組合物及可增加該FeO之預定量之第一還原劑之成分;將第二還原劑添加至該玻璃批料物質,其量等於在爐中增加熔融玻璃中之FeO達預定時間段之該第一還原劑的量之一或兩倍,及在該預定時間段之後停止前述步驟之實施。
- 如請求項1之玻璃組合物,其中該氧化劑為氧化鈰與氧化錳之混合物,其中鈰及錳氧化物之總濃度係在0.02至0.675%範圍內。
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2017
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US20200283330A1 (en) | 2020-09-10 |
CN104136386A (zh) | 2014-11-05 |
TW201343589A (zh) | 2013-11-01 |
CN104136386B (zh) | 2018-06-05 |
CA2864823A1 (en) | 2013-08-29 |
US11150389B2 (en) | 2021-10-19 |
RU2580857C1 (ru) | 2016-04-10 |
EP3572382A1 (en) | 2019-11-27 |
US20140029088A1 (en) | 2014-01-30 |
EP3572382B1 (en) | 2024-10-02 |
US20190101733A1 (en) | 2019-04-04 |
EP2817267B1 (en) | 2019-08-21 |
EP2817267A1 (en) | 2014-12-31 |
JP2015509477A (ja) | 2015-03-30 |
JP5927308B2 (ja) | 2016-06-01 |
US9658437B2 (en) | 2017-05-23 |
US10613304B2 (en) | 2020-04-07 |
US11754764B2 (en) | 2023-09-12 |
US20220075105A1 (en) | 2022-03-10 |
US20170227743A1 (en) | 2017-08-10 |
CA2864823C (en) | 2017-08-22 |
WO2013126282A1 (en) | 2013-08-29 |
US10191256B2 (en) | 2019-01-29 |
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