WO1999048825A1 - A medium gray colored glass with improved uv and ir absorption and nitrate-free manufacturing process therefor - Google Patents
A medium gray colored glass with improved uv and ir absorption and nitrate-free manufacturing process therefor Download PDFInfo
- Publication number
- WO1999048825A1 WO1999048825A1 PCT/GB1999/000483 GB9900483W WO9948825A1 WO 1999048825 A1 WO1999048825 A1 WO 1999048825A1 GB 9900483 W GB9900483 W GB 9900483W WO 9948825 A1 WO9948825 A1 WO 9948825A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- grey
- oxide
- glass composition
- less
- Prior art date
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- 239000011521 glass Substances 0.000 title claims abstract description 139
- 238000010521 absorption reaction Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000003086 colorant Substances 0.000 claims abstract description 35
- 239000011669 selenium Substances 0.000 claims abstract description 35
- 238000002834 transmittance Methods 0.000 claims abstract description 32
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 28
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000005284 excitation Effects 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 96
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 42
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 36
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 17
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 150000002697 manganese compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 230000003595 spectral effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000006060 molten glass Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000005315 stained glass Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006121 base glass Substances 0.000 claims 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 claims 1
- 150000001869 cobalt compounds Chemical class 0.000 claims 1
- 229940065287 selenium compound Drugs 0.000 claims 1
- 150000003343 selenium compounds Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 40
- 229940091258 selenium supplement Drugs 0.000 description 25
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000000156 glass melt Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- 239000005361 soda-lime glass Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000005816 glass manufacturing process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 3
- 239000003830 anthracite Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910000423 chromium oxide Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000010459 dolomite Substances 0.000 description 3
- 229910000514 dolomite Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006105 batch ingredient Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010434 nepheline Substances 0.000 description 2
- 229910052664 nepheline Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010435 syenite Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- AKLNLVOZXMQGSI-UHFFFAOYSA-N bufetolol Chemical compound CC(C)(C)NCC(O)COC1=CC=CC=C1OCC1OCCC1 AKLNLVOZXMQGSI-UHFFFAOYSA-N 0.000 description 1
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011565 manganese chloride Substances 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical class [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000439 uranium oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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
- 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
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C4/02—Compositions for glass with special properties for coloured 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
- C03C4/08—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/904—Infrared transmitting or absorbing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/905—Ultraviolet transmitting or absorbing
Definitions
- the invention is directed to a medium grey glass composition having improved UV and IR absorption while maintaining high visible light transmission and which may be manufactured without the use of sodium or potassium nitrate. More particularly, it is a soda-lime-silica glass whose colorants include iron oxide, selenium, manganese oxide, cobalt oxide, and optionally titanium oxide.
- Grey glass has found particular utility for architectural applications as building glass and has been considered for automotive glass applications.
- Glass is generally defined by certain spectral properties like dominant wavelength (colour), excitation purity, and light transmission.
- colour dominant wavelength
- excitation purity the higher the excitation purity of a colour, the closer it is to being a so-called neutral colour which does not distort the hues of objects seen through it.
- Those skilled in the art know that dominant wave- length, purity and light transmission all vary unpredictably with one another. Consequently, developing a new glass composition having a particular colour, purity and light transmission value is generally difficult. For example, an experimental change in the amount or relative proportions of one or more colorants in a glass composition intended to bring one of these numerical values closer to a target value may cause one or both of the other values to drift off target.
- the particular portions of the colorants is critical to developing a particular glass composition.
- Numerous different patented grey glasses have been manufactured by using as colorants iron oxide, cobalt oxide, and chromium oxide, selenium or nickel oxide. These same colorants have also been used to make glasses of colours other than grey, as would be appreciated however, at least one or more colorants being in different amounts.
- a brown or bronze glass can be made from iron oxide, cobalt oxide, and selenium, while the glass can be - 2 -
- US Patent 4,104,076 discloses a grey glass composition whose colorants consist essentially of: iron oxide, cobalt oxide, and selenium, where to avoid using nickel oxide, either or both chromium oxide or uranium oxide are employed. Cheng in US Patent 5,278,108, in contrast, forms a grey glass with colorants iron oxide, cobalt oxide, and selenium, specifically avoiding constituents that are disclosed to cause difficulty in manufacturing, i.e., chromium and manganese. In US Patent 4,873,206, a dark grey nickel-free glass is manufactured using iron oxide, cobalt oxide, and selenium, therein it is disclosed that the composition is to be essentially free of chromium, titanium, and manganese.
- UV and IR absorbing properties are excellent ultraviolet (UV) and infrared (IR) absorbing properties and very low excitation purity.
- UV ultraviolet
- IR infrared
- This low excitation purity makes the glass ideally suited for both automotive and architectural application since it has a neutral appearance favoured by designers.
- UV and IR absorbing properties make it ideally suitable to prevent colour fade damage to components inside a car or building and to keep the interiors cool.
- the UV and IR light absorption properties are especially valuable when the glass is for buildings since when heat is absorbed by the glass, the load on building air conditioners is reduced. Therefore, developing a glass with these spectral properties is very important.
- the present invention is a medium grey soda-lime-silica glass composition having excellent ultra violet and infra red absorbing ability.
- the colorants of the glass composition consist essentially of: greater than 0.5 and less than 0.9 wt. % total iron oxide as Fe 2 0 3 ; 0.1 to 1.0 wt . % manganese compound as Mn0 2 ; 0.0005 to 0.003 wt . % selenium - 4 -
- the glass composition having, at 4.0 mm. thickness: 485-570 dominant wavelength, less than 5% purity of excitation, 35 to 60% light transmittance using Illuminant A, less than 40 % ultra violet transmittance measured over 300-400 nm, and less than 45 % infra red transmittance measured over 760-2120 nm.
- the medium grey composition comprises by weight: 68 to 75% Si0 2 , 10 to 18% Na 2 0, 5 to 15% CaO, 0 to 10% MgO, 0 to 5% A1 2 0 3 , and 0 to 5% K 2 0, where CaO + MgO is 6 to 15% and Na 2 0 + K 2 0 is 10 to 20.
- the glass may also include tramp materials which sometimes enter the glass with raw materials or as a result of changeover of one glass composition to another in a glass furnace. For example, this would include up to about 0.005 wt . % nickel oxide as NiO.
- the glass composition has improved UV and IR absorption and a good shading coefficient, while maintaining good visible light transmittance.
- the new invention composition can be manufactured with little or no added sodium or potassium nitrate during melt processing. It has long been taught in the industry that such nitrates are to be added to maintain oxidising conditions and to decrease the volatilisation of selenium. Avoiding the use of nitrates advantageously curtails the production of N0 X emissions from these nitrates.
- Flat soda-lime-silica glass used in the automotive and architectural industries and conveniently made by the well known float glass process, is generally characterised by the following basic composition shown in Table I, the amounts of the components being based on a weight percentage of the total glass composition:
- the medium grey colour glass composition of the present invention employs this basic soda-lime-silica glass composition wherein, additionally, CaO + MgO is 6 to 15% and Na 2 0 + K 2 0 is 10 to 20%.
- the colouring components of the grey glass composition consists essentially of: total iron oxide as Fe 2 0 3 in an amount of greater than 0.5 and less than 0.9 wt. %, 0.1 to 1.0 wt. % manganese oxide as Mn0 2 , 0.002 to 0.010 wt . % cobalt oxide as Co, and 0.0005 to 0.003 wt . % selenium as Se.
- the glass considered at a 4.0 mm.
- thickness has the following spectral properties: 485 - 570 dominant wavelength, less than 5% purity of excitation, 35 to 60% light transmittance using Illuminant A, less than 40 % ultra violet transmittance measured over the range of 300 to 400 nanometers, and less than 45 % infra red transmittance measured over the range of 760 to 2120 nanometers.
- the dominant wavelength is between 485 and 560 nanometers, more preferably 485 to 520. - 6 -
- the materials are mixed and melted together to form the glass.
- sheet glass is made according to the well know float glass process.
- Melting and refining aids are routinely included in glass manufacture and may also be used herein.
- One refining aid generally used to remove bubbles from the glass is sodium sulphate which results in S0 3 in the glass.
- S0 3 is present in the glass composition at 0.10 to 0.30 wt. %, more preferably 0.14 to 0.25 wt.%.
- One required colorant, iron oxide as total iron oxide as Fe 2 0 3 is present in the invention grey glass composition in quantities in a range of greater than 0.5 but less than 0.9 wt.
- this colorant is added into the batch ingredients in the oxide form, Fe 2 0 3 .
- Fe 2 0 3 As discussed above, iron oxide exists in two forms in the glass melt. The oxidised form absorbs UV light and the reduced form absorbs infra red light, hence lowering the UV and IR transmittance through the glass products. Both absorbing functions of the iron oxide are especially valuable when the glass product is used in architectural applications particularly in geographic areas having significant sunshine.
- the ratio of the reduced iron oxide to the total iron oxide, FeO/total iron as Fe 2 0 3 is called the redox ratio of the iron oxide.
- the redox ratio of the iron oxide In the present glass it is preferably from 0.18 to 0.29, more preferably being from 0.20 to 0.26.
- the optimal redox ratio in the final product is determined by the particular spectral properties of the desired glass.
- Another essential colorant in the grey glass composition is a manganese compound, such as Mn0 2 .
- the manganese compound is present in the invention composition in an amount of 0.10 to 1.0 wt . % based on Mn0 2 , more preferably being 0.2 to 0.8 wt . %.
- This manganese compound can be added to the batch glass components in a variety of - 7 -
- manganese oxide or manganese carbonate compounds in the batch.
- a mixture of such compounds may also be employed.
- grey glass a naturally occurring mineral, pyrolusite, can be used to supply manganese dioxide to the batch.
- This mineral is advantageously used because the impurities within the mineral deposits are also those included in the present invention glass such as Fe 2 0 3 , A1 2 0 3 , Si0 2 , BaO, and CaO. Pyrolusite thus can effectively be used in the batch mixture as the source of manganese oxide and at a significant savings in batch cost.
- this colorant is generally present in the Mn +2 and Mn +3 state, although it may additionally be present in other states such as Mn +4 .
- One form of manganese oxide absorbs in the same area as selenium colorant so that it can desirably be used to replace selenium in providing the desired grey colour. Selenium is expensive and easily volatilised from the glass melt.
- Manganese oxide is inexpensive and not subject to such volatility so that it is optimal as a colorant in the present grey glass composition.
- the manganese colorant has oxidising ability so that when it is added it is able to shift the redox equilibrium of the iron oxide toward its less coloured oxidised form.
- manganese oxide is converted to the more colourless, reduced MnO.
- the following example shows the improved properties of the present medium grey invention glass as compared to a conventional grey glass.
- a conventional grey glass including iron oxide as a colorant ordinarily has a UV transmittance of about 44.4 % and an IR transmittance of 53.6 % at 56.8 % LTA (visible light transmission).
- a present invention embodiment with a deeper grey colour can be made having at almost identical 56.3 % LTA, while also exhibiting a significantly improved (i.e., decreased) UV transmittance of only 34.3 % and an IR transmittance of only 36.4 %.
- This particular example of a present invention embodiment makes visible the advantage of the present invention glass for architectural applications is apparent.
- manganese oxide colorant which additionally provides oxidising benefits, allows the elimination of sodium nitrate as a raw material component in the manufacture of the present invention grey glass.
- Manganese oxide which we believe aids in adjusting the oxidation state of iron oxide in the glass, also allows the use of anthracite coal to enhance the decomposition of sodium sulphate and improving the fining (removal of gaseous inclusions) characteristics of the glass batch.
- a reducing agent such as - 9 -
- anthracite coal A key preferred embodiment of the instant invention is combining in the batch manganese oxide with anthracite coal or other like reductants such as graphite, slag from coal fired furnaces, blast furnace slag, coke, or the carbonaceous materials.
- increasing manganese oxide will cause the iron oxide equilibrium in the melt to shift toward the oxidised form of the iron while the reductant reacts with the sodium sulphate to decompose into sodium oxide that becomes a part of the glass and sulphur trioxide that provides the fining action at lower temperatures.
- Sodium sulphate requires higher melting temperatures when a reductant is absent in the batch.
- the use of a reducing agent in the batch permits lower furnace operating temperatures while making a glass product with the same quality as glass made without the reductant at those higher temperatures. This methodology, we believe, has significant commercial and environmental benefits.
- Cobalt is a colorant used in the present invention grey glass composition. It is typically added to the batch ingredients as an oxide thereof, and is present as a colouring component in the glass in an amount of 0.002 to 0.01 wt. % as Co, preferably in an amount of 0.004 to 0.009 wt . %.
- the cobalt functions to absorb light in the 580 to 680 nanometer range of the visible spectrum.
- Cobalt has the function of lowering the % LTA and to balance the amount of absorption from Se, Mn0 2 and both FeO and Fe 2 0 3 to achieve the desired grey appearance of the present glass composition.
- the glass composition also includes selenium in an amount from 0.0005 to 0.003 wt . % as Se which is an essential ingredient for the grey colour because selenium has a maximum absorption about 500 nanometers and also combines with iron oxide to form an iron-selenium complex with a stronger absorption peak at about 490 nanometers.
- selenium in the Mn +3 form also has an absorption peak about 490 nanometers so that manganese oxide can partially replace selenium in the composition and - 10 -
- Selenium can be added to the glass in a variety of manners including: the elemental metal and in any compound form such as sodium selenite, barium selenite, selenium oxide, sodium selenate, etc.
- the present glass composition is able to attain excellent UV properties without the costly additives often used in other glass compositions for this purpose like titanium oxide, chromium oxide, cerium oxide or vanadium pentoxide.
- titanium oxide in an amount up to 1.0 wt . % can be added. It is known in the glass industry that titanium dioxide often enters glass compositions as a tramp material or impurity with raw materials when making soda-lime-silica glass compositions, e.g., with the sand, dolomite or limestone.
- the level of impurity that generally is present ranges normally from about 0.015 to about 0.05 wt.%, depending of the source of the individual raw materials. Thus, typically about 0.02 wt . % of titanium oxide will be present in a manufactured glass even when no titanium oxide has been intentionally added as a colorant to the glass melt.
- tramp materials may also enter the glass batch from changeover of the glass melting furnaces from one composition to another.
- the glass composition may also include tramp materials or impurities which often accompany the raw materials used. These tramp materials or impurities are expected to be in small amounts, e.g., up to 0.005 wt . % nickel oxide as NiO.
- inclusion of a manganese compound in glass has been found to reduce nickel sulphide stone formation.
- tramp materials like chromium, cobalt which might enter in glass making operation and which may be present in the described invention grey glass will be apparent to those skilled in the art in view of the present disclosure.
- the glass is made by mixing and melting the components, and expected to be manufactured according to well known glass making techniques, usually including continuously supplying the components to a melting furnace and heating the materials generally about 1500°C to make them molten and refining the glass. Then, this molten glass is formed into a glass sheet having a predetermined thickness by a float process or the like. Well known in the industry if the use of the molten tin baths for floating the glass.
- the glass compositions made in the examples are made according to the preferred invention manufacturing process, i.e., without the use of sodium nitrate as a component. It is unexpected and most desirable that the grey glass composition can be manufactured without the use of the commonly employed oxidant, sodium (or potassium) nitrate, however as discussed above the invention is not so limited. The glass can also be manufactured with the use of nitrates. We believe that the use of the colorant manganese compound allows for the manufacture of the glass without the addition of nitrate since the manganese compound colorant is also able to - 12 -
- the glass of the present invention may also be provided with a coating to vary the spectral properties is as often done in the industry, e.g., to modify the appearance colour or vary the reflectance of the glass with materials like chrome, iron, cobalt, or titanium. Still other coatings which may be applied to glass for these purposes would be apparent to those skilled in the art in view of the present disclosure.
- Examples of present invention glass composition embodiments were made in the lab according to the following procedure: batches were weighed, placed into a glass jar about 2" high and 2" inside diameter and dry mixed for 10 minutes each on a Turbula mixer, dry batch was placed into an 80% platinum/20% rhodium crucible that stands 2" tall and has an inside diameter at the top of 2.5" and is tapered to the base which has an inside diameter of 1.75". An amount of 4.5 ml. of water is added to the dry batch in the crucible and mixed with a metal spoon. After such preparation, a group of six different batches is melted in a gas/air fired furnace at the same time for 1 hour at 2600°F and each crucible is removed in turn from the furnace and fritted. Friting the glass involves coating the inside of the platinum/rhodium crucible with the molten glass and then plunging the crucible into cold water.
- All the laboratory melts made with the above procedure use a base composition of 100 grams sand, 32.22 grams of soda ash, 8.81 grams of limestone, 23.09 grams of dolomite, 1.2 grams of sodium sulphate, 0.075 grams of carbocite, 2.64 grams of nepheline syenite, and the remainder of the batch includes rouge, selenium, manganese dioxide and cobalt oxide in some example melts.
- Sodium nitrate was not included as a component in any of the examples.
- Table III shows the improvement of the ultra violet and infra red absorption of embodiments of present invention glass compositions as the iron oxide is increased and is shifted to its oxidised form by the addition of varying amounts of manganese dioxide. All of the examples display the calculated quantities of each colorant from the batch. For comparison, Example 1 is a commercially made product from Ford Motor Company called Sunglas® Grey. All of the selenium contents of the examples are the target values from batch based on 10 to 20% selenium retention. Iron oxide, manganese dioxide, and cobalt oxide in the examples are also the target values from the batch. - 14 -
- Table V further demonstrates the ultra violet absorption and infra red improvements attained when Mn0 2 and Fe 2 0 3 are steadily increased in invention example embodiments. - 16 -
- Example 17 from Table V represents an important embodiment of the present invention wherein the manganese dioxide has been increased, the glass has remained grey colour, evidenced by the low % excitation purity, and both the ultra violet and infra red absorption has steadily been improved. Note also that manganese dioxide can replace some of the selenium as in Examples 17 and 19 while maintaining the grey colour.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000537814A JP4454150B2 (en) | 1998-03-26 | 1999-02-15 | Medium gray colored glass with excellent UV and IR absorption |
EP99905067A EP1068156A1 (en) | 1998-03-26 | 1999-02-15 | A medium gray colored glass with improved uv and ir absorption and nitrate-free manufacturing process therefor |
KR1020007010597A KR20010034662A (en) | 1998-03-26 | 1999-02-15 | A Medium Gray Colored Glass with Improved UV and IR Absorption and Nitrate-Free Manufacturing Process Therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/048,649 US5977002A (en) | 1998-03-26 | 1998-03-26 | Medium gray colored glass with improved UV and IR absorption and nitrate-free manufacturing process therefor |
US09/048,649 | 1998-03-26 |
Publications (1)
Publication Number | Publication Date |
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WO1999048825A1 true WO1999048825A1 (en) | 1999-09-30 |
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ID=21955686
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1999/000483 WO1999048825A1 (en) | 1998-03-26 | 1999-02-15 | A medium gray colored glass with improved uv and ir absorption and nitrate-free manufacturing process therefor |
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Country | Link |
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US (3) | US5977002A (en) |
EP (1) | EP1068156A1 (en) |
JP (1) | JP4454150B2 (en) |
KR (1) | KR20010034662A (en) |
WO (1) | WO1999048825A1 (en) |
Cited By (1)
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FR2847573A1 (en) * | 2002-11-21 | 2004-05-28 | Visteon Global Tech Inc | COMPOSITION OF GRAY AND BRONZE GLASS |
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US6344271B1 (en) * | 1998-11-06 | 2002-02-05 | Nanoenergy Corporation | Materials and products using nanostructured non-stoichiometric substances |
US6652967B2 (en) * | 2001-08-08 | 2003-11-25 | Nanoproducts Corporation | Nano-dispersed powders and methods for their manufacture |
US5977002A (en) * | 1998-03-26 | 1999-11-02 | Ford Motor Company | Medium gray colored glass with improved UV and IR absorption and nitrate-free manufacturing process therefor |
DE10042771B4 (en) * | 2000-08-31 | 2004-02-12 | Schott Glas | Process for controlling and setting the redox state of redox refining agents in a glass melt |
US6777164B2 (en) * | 2001-04-06 | 2004-08-17 | Kodak Polychrome Graphics Llc | Lithographic printing forms |
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US7094716B2 (en) * | 2002-10-04 | 2006-08-22 | Automotive Components Holdings, Llc | Green glass composition |
US7708974B2 (en) * | 2002-12-10 | 2010-05-04 | Ppg Industries Ohio, Inc. | Tungsten comprising nanomaterials and related nanotechnology |
US6995102B2 (en) * | 2003-07-16 | 2006-02-07 | Visteon Global Technologies, Inc. | Infrared absorbing blue glass composition |
US7188489B2 (en) * | 2005-04-12 | 2007-03-13 | Martello Russell A | Portable air conditioner |
FR2886935B1 (en) * | 2005-06-10 | 2007-08-10 | Saint Gobain | GLASS SUBSTRATE WITH LOW INFRARED TRANSMISSION FOR DISPLAY SCREEN. |
US7560404B2 (en) * | 2005-09-08 | 2009-07-14 | Ppg Industries Ohio, Inc. | UV absorbing gray glass composition |
US7585801B2 (en) * | 2005-11-02 | 2009-09-08 | Ppg Industries Ohio, Inc. | Gray glass composition |
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US20070213197A1 (en) * | 2006-03-13 | 2007-09-13 | Boulos Edward N | Aqua blue glass composition with increased infrared absorption |
JP5109162B2 (en) * | 2006-03-27 | 2012-12-26 | 旭硝子株式会社 | Glass manufacturing method |
JP2008081333A (en) * | 2006-09-26 | 2008-04-10 | Furukawa Electric Co Ltd:The | Method for manufacturing glass strip |
US7932198B2 (en) * | 2007-09-04 | 2011-04-26 | Guardian Industries Corp. | Grey glass composition |
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WO2017073566A1 (en) * | 2015-10-28 | 2017-05-04 | 旭硝子株式会社 | Soda-lime glass |
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-
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- 1999-02-15 JP JP2000537814A patent/JP4454150B2/en not_active Expired - Lifetime
- 1999-02-15 EP EP99905067A patent/EP1068156A1/en not_active Withdrawn
- 1999-02-15 WO PCT/GB1999/000483 patent/WO1999048825A1/en not_active Application Discontinuation
- 1999-02-15 KR KR1020007010597A patent/KR20010034662A/en not_active Application Discontinuation
- 1999-07-29 US US09/354,857 patent/US6170292B1/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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US6170292B1 (en) | 2001-01-09 |
EP1068156A1 (en) | 2001-01-17 |
US5977002A (en) | 1999-11-02 |
US6035665A (en) | 2000-03-14 |
KR20010034662A (en) | 2001-04-25 |
JP4454150B2 (en) | 2010-04-21 |
JP2002507539A (en) | 2002-03-12 |
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