CN104136386B - 具有高氧化的铁含量的含锂玻璃及其制造方法 - Google Patents
具有高氧化的铁含量的含锂玻璃及其制造方法 Download PDFInfo
- Publication number
- CN104136386B CN104136386B CN201380010473.3A CN201380010473A CN104136386B CN 104136386 B CN104136386 B CN 104136386B CN 201380010473 A CN201380010473 A CN 201380010473A CN 104136386 B CN104136386 B CN 104136386B
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- Prior art keywords
- glass
- lithium
- glass composition
- composition according
- oxide
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 96
- 229910052742 iron Inorganic materials 0.000 title claims description 47
- 239000006123 lithium glass Substances 0.000 title abstract description 103
- 238000004519 manufacturing process Methods 0.000 title abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title description 11
- 230000003647 oxidation Effects 0.000 title description 10
- 239000011521 glass Substances 0.000 claims abstract description 107
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 78
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 43
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 42
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 41
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 17
- 230000005540 biological transmission Effects 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 3
- 241001269238 Data Species 0.000 claims description 2
- 230000003595 spectral effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 12
- 230000004297 night vision Effects 0.000 abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 238000005816 glass manufacturing process Methods 0.000 abstract description 4
- 238000005496 tempering Methods 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 36
- 230000008018 melting Effects 0.000 description 34
- 101000842368 Homo sapiens Protein HIRA Proteins 0.000 description 29
- 102100030473 Protein HIRA Human genes 0.000 description 29
- 230000000694 effects Effects 0.000 description 29
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 24
- 239000006066 glass batch Substances 0.000 description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 13
- 239000000523 sample Substances 0.000 description 10
- 239000005357 flat glass Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 5
- 238000007496 glass forming Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 239000005329 float glass Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000005368 silicate glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013068 control sample Substances 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000005347 annealed glass Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000038 blue colorant Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- HDXXSUQVQKJEBI-UHFFFAOYSA-N carbonic acid;cerium Chemical compound [Ce].OC(O)=O HDXXSUQVQKJEBI-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling 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
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229950008475 oxophenarsine Drugs 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- G02B5/226—Glass filters
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- 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
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- 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
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- 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
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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
- B32B17/10128—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—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
-
- 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
- C03C4/10—Compositions for glass with special properties for infrared transmitting 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
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Abstract
一种低红外线吸收性锂玻璃，其包括0.0005‑0.015wt％，更优选0.001‑0.010wt％的FeO，并且氧化还原比是0.005‑0.15，更优选0.005‑010。该玻璃可以化学回火和用于提供夜视镜或者显示器所用的冲击观察罩。提供了一种方法，通过将另外的氧化剂加入到批料中，来将玻璃制造方法从制造高红外线吸收性锂玻璃(其的FeO是0.02‑0.04wt％和氧化还原比是0.2‑0.4)变成低红外线吸收性锂玻璃。提供了第二方法，通过将另外的还原剂加入到该批料中，来将玻璃制造方法从制造低红外线吸收性锂玻璃变成高红外线吸收性锂玻璃。在本发明的一种实施方案中，该氧化剂是CeO2。本发明的一种实施方案包括根据所述方法制造的玻璃。
Description
交叉参考的相关申请
本申请要求2012年2月24日提交的，名称为“LITHIUM CONTAINING GLASS WITHHIGH OXIDIZED IRON CONTENT AND METHOD OF MAKING SAME”的美国临时专利申请系列No.61/602909的权益。申请系列号61/602909以其整体在此引入作为参考。
发明背景
发明领域
本发明涉及具有高氧化的铁含量的玻璃，和涉及制造这样的玻璃的方法，和更具体的，涉及一种方法，其将制造高红外线吸收性玻璃(即，具有高减少的铁含量的玻璃)的活动改变成制造低红外线吸收性玻璃(即，具有低减少的铁含量的玻璃)的活动，和由此制造的玻璃。这里还公开的是一种方法，其将制造低红外线吸收性玻璃(即，具有低减少的铁含量的玻璃)的活动改变成制造高红外线吸收性玻璃(即，具有高减少的铁含量的玻璃)的活动，和由此制造的玻璃。作为此处使用的，术语“活动”表示使用预定量的玻璃批料或成分来制造预定量的玻璃，例如但不限于平玻璃带，其具有预定的一系列性能，例如但不限于光学和着色性能。
技术讨论
在下面的讨论中特别关注的是含锂玻璃的制造。作为本领域技术人员所理解的，含锂玻璃通常用作基底来制造离子交换的增强玻璃。一种类型的含锂玻璃公开在美国专利No.4156755中(“下文称作USPN‘755“)，该专利在此引入作为参考。
通常，铁不是制造离子交换方法所用的含锂玻璃所需的成分，但是少量铁通常作为玻璃批料成分中的杂质而存在于含锂玻璃中，或者铁被加入到玻璃批料中来提供具有期望性能的含锂玻璃，例如但不限于光学和/或着色性能。作为市售玻璃中的Fe2O3的总氧化铁含量取决于产品要求，但是通常是50-1200份/百万{下文也称作“PPM”}或者0.005-0.12％的总铁，基于氧化物的重量(下文也称作“重量百分比”或“wt％”)，其被认为是透明玻璃组合物。更具体的，铁的加入可以作为亚铁的铁(FeO)或者作为三价铁的铁(Fe2O3)来进行。在玻璃批料熔融期间，在三价铁形式的铁(Fe+++)和亚铁形式的铁(Fe++)之间达到平衡，并且具有大约25-30wt％的亚铁形式的铁(Fe++)和70-75wt％的三价铁形式的铁(Fe+++)。氧化铁Fe2O3是一种强紫外线辐射吸收剂，并且作为黄色着色剂用于玻璃中，和氧化亚铁FeO是一种强红外线辐射吸收剂，并且作为蓝色着色剂用于玻璃中。在本发明的讨论中特别令人关注的是氧化亚铁FeO。
在加热玻璃片的情况中，例如但不限于所述讨论，在加热含锂玻璃片(下文也称作“锂玻璃片”)时，例如但不限于所述讨论，在弯曲和成形之前，该锂玻璃片的组合物通常包括0.02-0.04wt％的氧化亚铁(FeO)，和该锂玻璃片的氧化还原比(下面详细讨论)是0.2-0.4。在含锂玻璃(下文也称作“锂玻璃”)用于本发明的实践中作为红外线装置的观察窗(例如但不限于红外线夜视镜)，或者作为透明的装甲或者航天窗体的部件的情况中，该氧化亚铁优选的范围是0.001-0.010wt％，和该锂玻璃优选的氧化还原比是0.005-0.10。较高的氧化亚铁的wt％用于在加热锂玻璃片来增加红外线波长的吸收时，来降低锂玻璃片的加热时间以达到弯曲温度。较低的氧化亚铁的wt％用于根据本发明的教导，将锂玻璃用于红外线装置的观察窗，来增加红外线能量穿过该观察窗的透射百分率。
从制造高红外线吸收性(下文也称作“HIRA”)锂玻璃的活动变成制造低红外线吸收性(下文也称作“LIRA”)锂玻璃的活动，和/或从制造本发明的LIRA锂玻璃变成制造HIRA锂玻璃的活动的缺点之一是从一个活动结束时(例如制造HIRA锂玻璃的活动结束时)开始到接下来的活动开始时(例如制造LIRA锂玻璃的活动开始时)为止的期间所产生的玻璃的量，其满足LIRA锂玻璃或者HIRA锂玻璃的规格。处于作为LIRA锂玻璃和HIRA锂玻璃使用的规格之外的玻璃通常被废弃或者作为碎玻璃使用。现在本领域技术人员可以理解在从一个活动变到另一活动期间所制造的玻璃被废弃是昂贵的，这归因于锂玻璃相对高的批料成本和制造不可用的玻璃或者临界品质的玻璃所浪费的时间。
所以，有利的是提供一种方法，其使得与从制造可用的HIRA锂玻璃或者可用的LIRA锂玻璃的活动分别变成制造可用的LIRA锂玻璃或者可用的HIRA锂玻璃的活动相关的缺陷最小化或者消除该缺陷。
发明内容
本发明的一种非限定性实施方案涉及一种玻璃组合物，其包括下面的组分等：
和选自下面的氧化剂：大于0至0.50wt％的氧化铈、大于0至0.75wt％的氧化锰及其混合物，并且氧化还原比是0.005-0.15。
本发明的另一非限定性实施方案涉及一种用于观察辐射红外线能量的装置，该装置包含具有至少一个通路的外壳，该通路具有第一开口端和第二开口端，安装在该通路内用于观察辐射的红外线能量的透镜系统，改进包括：
与所述通路的一端相邻安装的化学回火冲击(ballistic)玻璃透镜，该冲击玻璃透镜包含第一表面，相对的第二表面和在该冲击玻璃透镜的第一和第二表面之间的玻璃段，该玻璃段包含下面的组分等：
和选自下面的氧化剂：大于0至0.50wt％的氧化铈、大于0至0.75wt％的氧化锰及其混合物，并且氧化还原比是0.005-0.15。
此外，本发明的另一种非限定性实施方案涉及一种方法，其用于在炉子中将熔融的玻璃从FeO为0.02-0.04wt％和氧化还原比为0.2-0.4的熔融的高红外线吸收性锂玻璃组合物改变为熔融的低红外线吸收性锂玻璃组合物，该熔融的低红外线吸收性锂玻璃组合物的FeO为0.0005-0.015wt％、氧化还原比为0.005-0.15和具有预定量的用于氧化FeO的第一氧化剂，该方法包括以下等：
供给玻璃批料，该玻璃批料具有提供熔融的低红外线吸收性锂玻璃组合物的成分，该组合物具有0.0005-0.015wt％的FeO，0.005-0.15的氧化还原比和预定量的用于氧化FeO的第一氧化剂；
以等于第一氧化剂的量的一倍或两倍的量，将第二氧化剂加入到该玻璃批料中预定的时间，以在炉子中氧化熔融玻璃中的FeO，和
在预定的时间之后，停止实施上面的步骤。
仍然此外的，本发明的一种非限定性实施方案涉及一种层合的透明体，例如飞机和陆地车辆挡风玻璃，其包含多个玻璃片，其中至少一个玻璃片是化学增强的和任选的塑料片，其中该玻璃片和塑料片通过塑料夹层层合在一起，并且至少一个玻璃片具有包括下面的组分等的玻璃组合物：
和选自下面的氧化剂：大于0至0.50wt％的氧化铈、大于0至0.75wt％的氧化锰及其混合物，并且氧化还原比是0.005-0.15。
另外本发明涉及一种方法，其用于在炉子中将熔融的玻璃从FeO为0.0005-0.015wt％，氧化还原比为0.005-0.10的熔融的低红外线吸收性锂玻璃组合物改变为FeO是0.02-0.04wt％和氧化还原比是0.2-0.4的高红外线吸收性锂玻璃组合物，该方法包括以下等：供给玻璃批料，该玻璃批料具有提供所述熔融的高红外线吸收性锂玻璃组合物的成分和预定量的第一还原剂来增加FeO；以等于第一还原剂的量的一倍或两倍的量，将第二还原剂加入到该玻璃批料中预定的时间，以在炉子中增加熔融玻璃中的FeO，和在预定的时间之后，停止实施前述的步骤。
附图说明
图1A和1B是玻璃熔炉的横截面的平面图，该炉子连接到用于根据本发明的教导来制造浮法玻璃带的类型的玻璃形成室上。
图2是图1A所示的玻璃熔融室的放大的横截面侧视图。
图3是显示了作为不同量的CeO2和MnO2氧化FeO的结果，氧化还原值和近似的亚铁铁(FeO)含量的图。
图4是显示了用不同量的CeO2和MnO2氧化亚铁铁(FeO)的图。
图5是本发明的夜视显示器的横截面侧视图，其具有根据本发明的教导所制造的保护性透镜。
图6是合并了本发明的特征的层合的冲击透镜或者床的侧面放大图。
发明详述
作为此处使用的，空间或方向术语例如“内部”，“外部”，“左边”，“右边”，“上”，“下”，“水平”，“垂直”等在它显示于附图的图上时涉及到本发明。但是，应当理解本发明可以假定不同的可选择的定向，并且因此这样的术语不被认为是限制性的。此外，用于说明书和权利要求中表示尺寸、物理特性等的全部数值被理解为在全部的情况中是用术语“大约”修正的。因此，除非有相反的指示，否则下面的说明书和权利要求中阐述的数值可以根据本发明所期望和/或所寻求获得的性能而变化。最起码，和并非打算使用等价原则来限制权利要求的范围，每个数字参数应当至少按照所报告的有效数字的数值和通过使用通常的四舍五入技术来解释。此外，这里公开的全部范围被理解为包含处于其中的任何的和全部的子范围。例如所述的范围“1-10”应当被认为包括了在最小1和最大值10之间(并包括其)的任何和全部子范围；即，全部的子范围是从最小值1或者更大开始，并且以最大值10或更低结束，例如1-6.7，或者3.2-8.1，或者5.5-10。同样，作为此处使用的，术语“安装于其上”表示安装于其上，但是不必需表面接触。例如，一个制品或者制品的部件“安装于”另一制品或者制品的部件之上不排除在制品之间或者制品的部件之间分别存在着材料。
在讨论本发明的几个非限定性实施方案之前，应当理解本发明并不将它的应用限制于这里所示和所讨论的具体的非限定性实施方案的细节，因为本发明能够是其他实施方案。此外，这里用于讨论本发明的术语是用于说明目的，而非限制。仍然此外的，除非另有指示，否则在下面的讨论中，同样的标记指的是同样的元件。
本发明的非限定性实施方案公开了使用USPN‘755所公开的锂玻璃组合物，但是，本发明不限于此，并且本发明可以实践来从一个活动(其制造苏打-石灰-硅酸盐玻璃，该玻璃具有高的氧化的铁含量，例如但不限于氧化亚铁的范围是0.02-0.04wt％，和氧化还原比的范围是0.2-0.4)变成另外一个活动(其制造苏打-石灰-硅酸盐玻璃，该玻璃具有低的氧化的铁含量，例如但不限于氧化亚铁的范围是0.001-0.010wt％，和氧化还原比的范围是0.005-0.15)。
如现在可以理解的，Fe2O3和/或FeO可以作为着色剂或者改性剂而加入。这里公开的锂玻璃中存在的铁的总量是以Fe2O3方面，根据常规的分析实践来表达的，但是并不意味着全部的铁实际上都处于Fe2O3的形式。同样，处于亚铁态的铁的量是作为FeO来报告的，即使它实际上不会作为FeO存在于玻璃中。为了反映这里公开的玻璃组合物中亚铁和三价铁的相对量，术语“氧化还原比”应当表示以FeO表达的处于亚铁态的铁的量除以以Fe2O3表达的总铁的量。此外，除非另有指示，在本申请中术语“总铁”应当表示以Fe2O3方面表达的总铁，和术语“FeO”应当表示以FeO方面表达的处于亚铁态的铁。
USPN‘755所公开的含锂玻璃的材料或成分的范围列于下表1中。
表1
该玻璃中除了锂之外全部的氧化物的重量百分比是使用X射线荧光光谱法(也称作“XRFS”来测量的)。氧化锂在该玻璃中的重量百分比是通过原子吸收来测量的。
也可以包括少量(高到总共大约5重量％)的其他玻璃形成材料和玻璃改性剂或着色剂，例如MgO，MnO，TiO2，Sb2O3，As2O3，K2O，PbO，ZnO和CaO及其混合物。如本领域技术人员所理解的，Sb2O3和As2O3是用于玻璃片牵引方法的氧化剂，但是不适用于浮法玻璃方法，这是因为浮法玻璃室的还原性条件将Sb2O3和As2O3分别还原成锑和砷金属。
在本发明的一种非限定性实施方案中，当加热具有表1的组成的锂玻璃片时，例如但不限于所述的讨论，在该片弯曲和/或成形之前，该锂玻璃组合物包含表1的成分加上0.02-0.05wt％和优选0.03-0.038wt％的氧化亚铁，并且氧化还原比是0.2-0.4和优选是0.2-0.35(下文中前述玻璃也称作“高红外线吸收性锂玻璃”或“HIRA锂玻璃”)。在制造HIRA锂玻璃的活动期间，将硫酸盐和碳添加到玻璃批料成分中。进行该硫酸盐和碳的添加来增加氧化亚铁含量，以将熔融的玻璃保持在期望的氧化还原比范围内。
在本发明的另一种非限定性实施方案中，当具有表1的组成的含锂玻璃被作为观察窗，用于红外线装置，例如但不限于红外线夜视镜，显示器例如来复枪显示器时，该锂玻璃组合物包含表1的成分。如所示的，铁的氧化物没有作为组分列出，但是如本领域技术人员所理解的，可以预期铁的氧化物例如亚铁的铁将作为批料例如碎玻璃中的随机材料存在于该玻璃中。在亚铁的铁可以存在的程度，本发明可以预期本发明的玻璃将包括表1的组合物加上0.0005-0.015wt％和优选0.001-0.010wt％的氧化亚铁，并且氧化还原比是0.005-0.15和优选是0.005-0.10(下文中前述玻璃也称作“低红外线吸收性含锂玻璃”或“LIRA锂玻璃”)。可以预期的是总铁(Fe2O3)将是50-200ppm的Fe2O3。在制造LIRA锂玻璃的活动期间，将与所选择的玻璃制造方法相容的氧化剂加入该玻璃中，例如将氧化铈，氧化锰，氧化锑，氧化砷及其组合物加入该玻璃批料成分中，来将熔融的玻璃保持在用于LIRA锂玻璃的氧化还原比范围内。
如上所述，对于HIRA锂玻璃来说，使用更高的wt％的氧化亚铁来增加红外线波长的吸收，来降低玻璃的加热时间，以达到弯曲温度或者来提供一定水平的太阳热控制，和对于LIRA锂玻璃来说，使用较低的wt％的亚铁铁来降低红外线观察范围内红外线能量的吸收，和增加红外线观察范围内红外线能量的透射百分率，以增强产生红外线的物体的观察。为了清楚起见，电磁频谱的紫外光波长范围是300-380纳米(下文也称作“nm”)；可见光波长范围是380-780nm；和近红外光波长范围是800-2100nm。该红外线观察波长范围是装置依赖性的。在本发明的一种非限定性实施方案中，电磁频谱的红外线观察波长范围是400-920nm。在本发明的实践中，该LIRA锂玻璃优选的可见光透射率等于和大于88％，更优选可见光透射率大于89％和最优选可见光透射率大于90％；红外线透射率等于和大于80％，更优选红外线透射率大于85％和最优选红外线透射率等于和大于90％；红外线观察透射率等于和大于80％，更优选红外线观察透射率大于85％和最优选红外线观察透射率大于90％。
此外，在本发明的实践中，该HIRA锂玻璃的可见光透射率小于88％；红外线透射率小于75％；红外线观察透射率小于80％。
上面给出的LIRA锂玻璃的光谱性能是以0.223英寸(5.7毫米)的厚度来报告的。可见光透射率是使用CIE标准光源A，以2°观察器在380-780nm波长范围上来报告的。红外线透射率是使用Parry Moon air mass 2.0直接太阳辐照数据，在800-2100nm的波长范围上来测定的。观察透射率是使用CIE标准光源A的相对分光照度和观察装置在400-930nm波长范围上的响应函数来测定的。
本发明的LIRA和HIRA锂玻璃可以使用常规的非真空精炼机浮法玻璃系统来制造，例如但不限于图1和2所示类型，或者使用真空精炼机浮法玻璃系统，例如但不限于美国专利No.4792536和5030594所公开的类型，该专利在此引入作为参考。
参见图1A，1B和2，常规的连续供料、十字槽点火的玻璃熔融和非真空精炼炉20包括由难熔材料制成的底部22、顶部24和侧壁26所形成的外壳。该HIRA或LIRA锂玻璃批料28是通过炉子20的扩展部32的入口30(参见图2，被称作填充投料口)，以任何方便的或者通常的方式引入，来形成漂浮于熔融玻璃38的表面36上的覆盖物34(参见图2)。图1A和1B所示的玻璃的整体行进在图中是从左到右的，朝着本领域制造浮法平玻璃所用类型的玻璃形成室40的入口端39(参见图1B)。
用于熔融批料28和加热熔融的玻璃38的火焰(未示出)从沿着侧壁26间隔的燃烧室口42发出(参见图2)，并且在熔融的玻璃38的表面36之上和沿着其引导。作为本领域技术人员已知的，在加热周期的第一个一半期间，火焰从槽子20一侧上的每个口中的喷嘴43(参见图2)中发出，而炉子废气移动穿过炉子对侧上的口。在加热周期的第二一半期间，所述口的功能反转，并且废气口是点火口，和点火口是废气口。图1A，1B和2所示类型的炉子的点火周期是本领域公知的，不再赘述。
如本领域技术人员可以理解的，本发明预期使用空气和燃料气体的混合物，或者氧和燃料气体的混合物，来产生火焰以加热批料和熔融的玻璃。对于在玻璃熔炉中使用氧和燃料气体的讨论来说，可以参考美国专利申请公开No.2009-0205711A1，标题为“Use ofPhotovoltaic for Waste Heat Recovery”，该公开内容在此引入作为参考。
从批料供料端或者投料端壁46下游移动的玻璃批料28是在炉子20的熔融区48中熔融的，并且该熔融的玻璃38移动穿过腰部54(参见图1B)到炉子20的精炼区56。在精炼区56中，除去熔融的玻璃38中的气泡，和将该熔融的玻璃38在该熔融的玻璃送过精炼区56时进行混合或均化。熔融的玻璃38是以任何方便的或者通常的方式，从精炼区56在玻璃形成室40所包含的熔融金属池(未示出)上传递的。在传递的熔融玻璃38在熔融金属池(未示出)上移动通过玻璃形成室40时，将该熔融的玻璃是尺寸化和冷却。维度稳定的尺寸化玻璃带(未示出)从玻璃形成室40移出进入退火玻璃韧化炉(未示出)。图1A，1B和2所示类型和上述类型的玻璃制造设备是本领域公知的，不再赘述。
作为本领域技术人员现在可以理解的，当从制造HIRA锂玻璃的活动变为制造LIRA锂玻璃的活动时，在制造HIRA锂玻璃的活动结束时炉子20所包含的熔融的HIRA锂玻璃中的亚铁的铁(参见图1A，1B和2)优选降低到0.0005-0.015wt％，和更优选到0.001-0.010wt％，和氧化还原比优选降低到0.005-0.15和更优选到0.005-0.10。在本发明的实践中，炉子中熔融的HIRA锂玻璃例如1850吨转化成熔融的LIRA锂玻璃是在3-4天内进行的，而通过仅仅加入无氧化剂的LIRA锂玻璃批料成分进行转化将需要大约两周。
在本发明的实践中，从熔融的HIRA锂玻璃变成熔融的LIRA锂玻璃可以在3-4天内，使用氧化剂来进行。在本发明的一个非限定性实施方案中，氧化铈(CeO2)和/或氧化锰(MnO2)被用于将亚铁的铁氧化成三价铁的铁，因为如上所述，它们是与图1A，1B和2所示的玻璃制造方法相容的。在本发明优选的实践中，氧化铈(CeO2)被用于将亚铁的铁氧化成三价铁的铁，这是因为氧化铈(CeO2)是比氧化锰(MnO2)更有效的氧化剂，如所进行的实验所示。
更具体的，制造了表2所示玻璃的样品(也称作“对照样品”)；表1所示的加入了CeO2的玻璃的样品(也称作“铈样品”)和表1所示的加入了MnO2的玻璃的样品(也称作“锰样品”)。样品1-5是铈样品，其具有不同量的氧化铈，和样品6和7是锰样品，其具有不同量的氧化锰。
图3是显示了氧化还原比和近似的FeO含量的图，和图4是显示了氧化亚铁含量的图，其是对照样品和样品1-7在坐标轴(y轴)上的含量，并且氧化铈和氧化锰的wt％在横坐标(x轴)上。对照样品数据点是在y轴上。在本发明优选的实践中，氧化铈被用于将亚铁的铁氧化成三价铁的铁，因为如图3和4所示，氧化铈是比氧化锰更有效的氧化剂，氧化铈“脱色”了该玻璃。更具体的，氧化铈不是玻璃中的着色剂，而氧化铈是玻璃中的强力氧化剂，并且它在脱色玻璃中的作用是将亚铁态的铁(Fe++)氧化成三价铁态的铁(Fe+++)。虽然氧化铈可用于脱色其余的痕量的亚铁铁，但是使用氧化铈具有局限，例如但不限于所述讨论，将LIRA锂玻璃曝露于日光对于该玻璃具有日晒效果，其导致Ce+++光氧化成Ce++++和Fe+++光还原成Fe++。如本领域技术人员所理解的，铈的日晒效应和Fe+++光还原成Fe++降低了透射率，和增加了玻璃在电磁频谱的可见光和IR范围内的吸收率。因为可见光和红外线透射率的下降小于1％，因此氧化铈优选氧化亚铁的铁。不过，本发明可预期加入氧化锰代替氧化铈和加入氧化锰和氧化铈的混合物。
在本发明的实践中，可以使用大于0至0.50wt％的氧化铈；优选0.02-0.45wt％，更优选0.04-0.40wt％。用于氧化铈的其他范围包括但不限于0.01-0.15wt％；0.02-0.10wt％和0.03-0.07wt％。可以使用大于0至0.75wt％的氧化锰，优选0.02-0.50wt％，和更优选的量是0.04-0.45wt％。可以理解的，CeO2和MnO2的混合物可以用于本发明的实践中来氧化亚铁的铁。通常对于给定范围的MnO2，一份的CeO2代替1.10-1.50份的MnO2，和对于给定范围的CeO2，1.10-1.5份的MnO2代替一份的CeO2。较低的总铁含量的玻璃可以使用较低量的氧化铈或者氧化锰。在本说明书中氧化铈或氧化锰的量应当分别表示总的铈或锰，以CeO2或MnO2方面来表达，即使这些组分实际上不会作为CeO2或MnO2存在于玻璃中也是如此。
在本发明下面的非限定性实施方案中，进行活动A来制造HIRA锂玻璃。活动A被指出终止时，开始活动B来制造LIRA锂玻璃。所制造的HIRA锂玻璃的组成和所制造的LIRA锂玻璃的组成显示在表3中。
表3
在活动A运行期间，将HIRA锂玻璃批料供入炉子20(参见图1A，1B和2)中，熔融，精炼和将精炼的玻璃如上所述移入玻璃形成室40中，来制造具有表3所示组成的HIRA锂玻璃。在活动A结束时的指定时间，将用于LIRA锂玻璃的玻璃批料如上所述移入炉子20的熔融区48中，来开始活动B。在活动B的第一个36小时期间，配制了用于LIRA锂玻璃的批料来提供锂玻璃，其氧化铈是0.04-0.90wt％，即，两倍于表3的锂玻璃所规定的氧化铈。在36小时期间之后，配制了用于LIRA锂玻璃的批料，来提供氧化铈为0.02-0.45wt％的锂玻璃(参见表3)。
在本发明的一种实施方案中，将碳酸铈加入该批料中来在玻璃中提供氧化铈。为了制造表3的LIRA锂玻璃，将0.033-0.75wt％的碳酸铈加入该批料中。使用初始的LIRA锂玻璃批料(活动B的第一个36小时期间)，将0.066-1.50wt％的碳酸铈加入该批料中。在活动B的初始36个小时时期结束时，将碳酸铈降低到0.033-0.75wt％来进行活动B，以制造表3的LIRA锂玻璃。在活动B的第一36个小时期间，使用另外的碳酸铈以在炉子20的熔融区26和精炼区56中氧化亚铁的铁。在初始的36个小时时期结束时，将用于LIRA锂玻璃的玻璃批料移入炉子20的熔融区46中，如上所述。
在本发明的另一种非限定性实施方案中，如果所制造的玻璃具有足够的UV吸收剂例如氧化铈，则在36小时脉冲后，如果使用足够低的铁批料，例如但不限于具有小于0.0005wt％的本发明的批料被用于制造不具有UV吸收剂的玻璃，则不需要另外加入碳酸铈。
本发明不限制所述脉冲数或长度，或者脉冲中氧化铈的wt％。在本发明的实践中，脉冲中氧化铈的wt％通常是LIRA锂玻璃批料中的氧化铈的wt％的2-3倍，并且脉冲数通常是1或2。每个脉冲的时间可以根据需要变化。当在本发明的实践中使用从活动A变到活动B，使用MnO2或者CeO2和MnO2的混合物，来从制造HIRA锂玻璃的活动A变成制造LIRA锂玻璃的活动B时，上述程序涉及到使用CeO2来氧化亚铁的铁。虽然程序是相同的，但是MnO2和CeO2和MnO2的混合物的wt％增加，这归因于氧化铈是一种比氧化锰更有效的氧化剂。
本发明不限于将氧化剂，例如但不限于CeO2，MnO2，和CeO2和MnO2的混合物加入到批料中，并且本发明预期将另外的氧化剂在精炼机56中加入到熔融的玻璃中或者在腰部54上游的位置在熔炉36中加入到熔融的玻璃中。
在本发明另外一种非限定性实施方案中，通过加入还原剂来将三价铁的铁还原成亚铁的铁，来将制造LIRA锂玻璃的活动变成制造HIRA锂玻璃的活动。可以用于本发明实践中的还原剂包括但不限于碳，含碳材料，例如但不限于石墨，蔗糖(C12H22O11)，煤，硅金属和氧化锡(SnO2)。本发明另外的非限定性实施方案包括但不限于将制造不同类型的苏打-石灰硅酸盐玻璃或者任何其他类型的玻璃的活动进行改变，例如从HIRA或者LIRA锂玻璃变成苏打-石灰硅酸盐玻璃的活动，反之亦然。
本发明在活动A和B期间使用HIRA锂玻璃和LIRA锂玻璃不限制本发明，并且可以加工来作为窗体，用于陆地、天空、太空、水上和水下，交通工具；作为透明片用于商业和住宅窗体，作为盖子用于太阳能收集器，和用于冲击观察窗。该HIRA锂玻璃通常用于观察窗，其使用了提供可见光的源，和通常不推荐用于观察来自物体的红外线能量，例如HIRA锂玻璃不推荐用于夜视镜。对于夜视装置，该LIRA锂玻璃被推荐来保护夜视装置的透镜系统，例如但不限于夜视镜和夜视显示器。更具体的和参考图5，显示了夜视来复枪显示器70，其具有管72和安装在管72的通路76中的夜视放大透镜系统74。由化学增强的LIRA锂玻璃制成的冲击透镜78安装在与透镜系统74隔开的管的一端处。使用这种排列，通过本发明的化学增强的LIRA锂玻璃透镜保护了透镜系统74防止破裂。LIRA锂玻璃也可以用于专业应用，包括但不限于本发明它在家具、器具和淋浴门中的应用。
参考图6，显示了冲击透镜或者窗84的一种非限定性实施方案。窗体84包括多个通过层合领域所用类型的塑料夹层材料90层合在一起的LIRA锂化学增强的玻璃片86和塑料片88。
在本发明的非限定性实施方案的实践中，LIRA和HIRA锂玻璃可以是未涂覆的或者涂覆有任何类型的涂层，例如但不限于选择性通过预定波长范围的光和能量的环境涂层，光催化膜或者减水膜，或者透明的传导氧化物例如公开在美国专利No.5873203和5469657中的类型，该专利在此引入作为参考。
本发明不限于所提出的和上面讨论的本发明的实施方案，其仅仅用于说明之目的而提出，并且本发明的范围仅仅受限于下面的权利要求和任何另外的加入本申请的权利要求(其具有属于本申请的直接的或者间接的子句)的范围。
Claims (9)
1.一种玻璃组合物，其由如下组成：
着色剂部分，其由如下组成：
FeO 0.0005-0.015wt％；
Fe2O3总铁 50-1200ppm；
并且氧化还原比范围在0.005-0.15，
和选自大于0至0.50wt％的氧化铈、大于0至0.75wt％的氧化锰及其混合物的氧化剂，
其中所述玻璃具有大于88％的可见光透射率，大于85％的红外线透射率，大于80％的红外线观察透射率，其中上面给出的玻璃的光谱性能是以0.223英寸的厚度来报告的，可见光透射率是使用CIE标准光源A以2°观察器在380-780nm波长范围上测定的，红外线透射率是使用Parry Moon air mass 2.0直接太阳辐照数据在800-2100nm的波长范围上来测定的，观察透射率是使用CIE标准光源A的相对分光照度和观察装置在400-930nm波长范围上的响应函数来测定的。
2.根据权利要求1的玻璃组合物，其中氧化铈范围在0.01-0.15wt％。
3.根据权利要求1的玻璃组合物，其中FeO范围在0.001-0.010wt％。
4.根据权利要求1的玻璃组合物，其中Fe2O3总铁范围在50-200ppm。
5.根据权利要求1的玻璃组合物，其中氧化还原比范围在0.005-0.10。
6.根据权利要求1的玻璃组合物，其中该氧化剂选自0.02-0.45wt％的氧化铈、0.02-0.50wt％的氧化锰及其混合物。
7.根据权利要求1的玻璃组合物，其中FeO范围在0.001-0.010wt％；总铁范围在50-200ppm；氧化还原比范围在0.005-0.10；以及氧化剂选自0.02-0.45wt％的氧化铈、0.02-0.50wt％的氧化锰及其混合物。
8.根据权利要求1的玻璃组合物，其中该氧化剂是氧化铈和氧化锰的混合物，其中氧化铈和氧化锰的总浓度范围在0.02-0.675％。
9.根据权利要求1的玻璃组合物，其中该玻璃为低红外线吸收性玻璃。
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| US61/602,909 | 2012-02-24 | ||
| US13/768,030 US9658437B2 (en) | 2012-02-24 | 2013-02-15 | Lithium containing glass with high oxidized iron content and having specified base, colorant, and oxidizer |
| PCT/US2013/026344 WO2013126282A1 (en) | 2012-02-24 | 2013-02-15 | Lithium containing glass with high oxidized iron content and method of making same |
| US13/768,030 | 2013-02-15 |
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