CN1043217C - 灰色玻璃组合物 - Google Patents
灰色玻璃组合物 Download PDFInfo
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- CN1043217C CN1043217C CN94118331A CN94118331A CN1043217C CN 1043217 C CN1043217 C CN 1043217C CN 94118331 A CN94118331 A CN 94118331A CN 94118331 A CN94118331 A CN 94118331A CN 1043217 C CN1043217 C CN 1043217C
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- 239000011521 glass Substances 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 239000005357 flat glass Substances 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000004040 coloring Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000006132 parent glass Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 26
- 239000011669 selenium Substances 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- 238000002834 transmittance Methods 0.000 abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000005352 clarification Methods 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000004458 analytical method Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000006124 Pilkington process Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- SXGROPYLQJYUST-UHFFFAOYSA-N iron(2+);selenium(2-) Chemical compound [Fe+2].[Se-2] SXGROPYLQJYUST-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- NCXOIRPOXSUZHL-UHFFFAOYSA-N [Si].[Ca].[Na] Chemical compound [Si].[Ca].[Na] NCXOIRPOXSUZHL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000006066 glass batch Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 239000000155 melt Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
- 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
- C03C4/02—Compositions for glass with special properties for coloured glass
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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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
本发明提供的玻璃组合物具有中性灰色，并且其透光率(可见光)使该玻璃组合物适合于在车辆中用作隐蔽窗玻璃。基础玻璃是一种钠钙硅组合物并添加铁、钴、硒和/或镍作为着色剂。在本发明的一个最佳实施方案中。通过使用下面的着色剂：0.820～0.935%的玻璃中所有的Fe2O3(总铁)，不高于0.30wt%FeO，60-180ppmCoO、0-30ppm Se和0-550ppmNiO，可获得厚度3.9mm时透光率(C.I.E.照明剂A)在20%-50%范围内的中性灰色玻璃。
Description
本发明涉及一种中性灰色玻璃；该玻璃所具有的透光率使它非常适合在车辆中(例如货车的后部)用作隐蔽窗玻璃。更具体地说，本发明的玻璃的透光率在20-50％范围内。通过使用铁、钴、硒和/或镍作为着色剂来获得需要的颜色和性能。此外，本发明的玻璃比用于汽车中的典型的绿色玻璃具有更低的红外和总太阳能透射率以降低车内获取的热量。这种玻璃还适合于平板玻璃的制造工艺。
本技术领域人们已经知道许多热吸收玻璃基片。典型的绿色汽车玻璃的主要着色剂是铁，它通常以Fe2O3和FeO的形式存在。通常玻璃中存在的铁的总量用Fe2O3表示，而不管其实际上存在的形式。典型的绿色汽车玻璃中总铁含量约0.50％(重量)，而FeO与总铁的比大约为0.25。
一些玻璃通过采用氧化镍作着色剂在玻璃中产生灰色(例如：Duncan等人的美国专利重新授权NO.25312)。然而，采用含镍物质必须小心地控制，因为熔化过程中镍的存在有时会导致玻璃中硫化镍结合的形成。使用镍时还可能面临的别的潜在问题包括：由于镍在锡槽中的还原在玻璃表面形成雾(haze)以及当对其进行热处理时玻璃颜色发生改变。
为了避免这些问题，人们开发了含有氧化铁，氧化钴和硒的无镍着色玻璃(如Duncan等人在美国专利NO.3296004、Kato等人在美国专利NO.3723142和Bamford在英国专利说明书1331492中公开的)，Pons在美国专利NO.4104076中用Cr2O3或UO2代替镍与氧化铁、氧化钴和硒结合使用来制备灰色玻璃。最近，Krumwiede等人在美国专利NO.5023210中公开了用氧化铁、氧化钴、硒和氧化铬为着色剂的无镍的灰色玻璃。
许多的市场上可买到的灰色玻璃都颜色太深以致于不能用在车辆的前视区。此外，这些玻璃还可能因颜色太深了以致于从车外不能看见安装在车内的安全灯光。因此很希望能有用于车辆隐蔽区的具有深灰色的中性灰色玻璃，它同时允许足够的安全灯光照明，并且具有稳定的颜色，还适合于工业化平板玻璃的制造技术。
本发明提供了一种具有中性灰色的玻璃组合物，其透光率(可见光)使该玻璃适合用于车辆中的隐蔽窗玻璃。本发明的玻璃具有标准的钠钙硅平板玻璃基础组成。现已发现通过使用下面的着色剂：0.15-1.2wt％的玻璃总Fe2O3量(总铁)，不高于0.30wt％的FeO,60-180PPm的CoO、0-30PPm的Se和0-500PPm的NiO，可获得在厚度为3.9mm时透光率(C.I.E.照明剂A)在20％-50％的中性灰色玻璃。这种玻璃组合物的一个最佳实施方案包括0.20-1.1wt％的Fe2O3、0.05-0.29wt％的FeO、62-170PPm的CoO和0-24PPm的硒和0-500PPm的NiO。
本发明玻璃的主波长根据具体的颜色选择可以有些变化。在本发明中，优选的玻璃是中性灰色玻璃，并具其特征在于主波长在480-580nm范围内、优选是485-540nm，而色纯度不超过8％，优选不超过3％。
本发明的基础玻璃即不包括着色剂的主要组成，是具有下面特征的工业化钠钙硅玻璃： 重量％
SiO2 66-75
Na2O 10-20
CaO 5-15
MgO 0-5
Al2O3 0-5
K2O 0-5
BaO 0-1
向本发明的这种基础玻璃中添加铁、钴、硒和/或镍形式着色剂。在本发明一个具体实施方案中，玻璃基本上是无镍的；即没有有意地添加镍或镍化合物，虽然由于掺杂引起的迹量的镍总是难免的。本发明的玻璃基本上没有其它的着色剂。但应该明白这里公开的玻璃组合物也可以包括少量的其它物质例如助熔剂和澄清剂、过程物质或杂质。这些物质可以包括(但不局限于)铬、锰、铈、钼、钛、氯、锌、锆、硫、氟、锂和锶。如同在后要详细讨论的，还应该明白这些物质中的一部分或其它物质可以加入到玻璃中以提高玻璃的太阳性能(Solar performance)。
硒着色剂在玻璃中形成粉红色，但当硒与铁铬合形成硒化铁(FeSe)时则产生棕色。钴形成蓝色，铁根据其氧化状态以不同比例可形成黄色和蓝色。如果使用，镍形成绿棕色至黄棕色。
本发明的玻璃可在一个连续大规模工业化熔化设备上进行熔化和澄清，通过浮法工艺(熔融玻璃支撑在熔融金属通常是锡的槽中)成型为各种厚度的平板玻璃板(假设为带状)并冷却。应该了解，由于在熔融锡上成型玻璃，在与锡接触的玻璃一侧的表面部分可能渗透了可测量到的氧化锡。典型地，与锡接触的玻璃表面的最初几个微米里，浮法玻璃片的SnO2的浓度至少为0.05wt％。
根据标准分析方法，玻璃中存在的铁的总量在这里用Fe2O3来表示，但并不表明所有的铁实际都是以Fe2O3的形式存在。同样地，以亚铁态存在的铁的含量用FeO来表示，虽然它实际上在玻璃中可能不是以FeO存在的。总铁量中以亚铁态存在的比例用来表征玻璃的氧化还原状态，并表示为FeO/Fe2O3比率，是用亚铁态铁的重量百分数(用FeO表示)除以总铁的重量百分数(用Fe2O3表示)。除非另有说明，本说明书中的术语Fe2O3指总铁(用Fe2O3表示)，术语FeO指亚铁态的铁(用FeO表示)。
本发明公开的玻璃组合物可以使用几种熔化装置的任何一种来制造但不局限于这些方法，例如本技术领域中众所周知的通用的上部烧成连续熔化工艺或在下面将详细讨论的多阶段熔化工艺。然而，对于氧化还原比低于0.30的玻璃组合物优选前一种工艺而对于氧化还原比等于或大于0.30的玻璃组合物优选后一种工艺。
传统的上部烧成连续熔化工艺的特征在于将配合料放置在保持在池式熔化炉中的熔融玻璃液流上并且施加热能直到该物质熔化到熔融玻璃液流中。该熔化池通常含有大量的熔融玻璃，从而使熔融玻璃的液流具有足够的流动滞留时间，以使玻璃在排放到成型工艺中之前达到一定程度的均化和澄清。
多阶段玻璃熔化和澄清工艺公开在Kunkle等人的美国专利4381934和4792536、Pecoraro等人的美国专利4792536和Cerutti等人的美国专利4886539中，其特征在于它有多个独立的阶段，从而可以对氧化还原条件提供更灵活的控制。在这些专利中公开的总熔化工艺包括三个阶段：液化阶段、溶化阶段和真空澄清阶段。在液化阶段中配合料(优选地以粉末状态)喂入旋转的筒形液化容器中。当该配合料在该容器中向热量暴露时，液化的物质从倾斜的配合料衬里上流到位于该容器底部的中央排料口中。液化物料流从该液化容器自由落下进入溶化阶段的溶化容器中。该溶化容器通过在与下游澄清阶段分开的一个位置提供一段停留时间而使来自液化阶段的液化物料中的未熔颗粒完全溶化。该溶化容器可以是水平伸长的耐火料盆形状，该料盆在其相对的两端具有进口和出口，用来确保适当的停留时间。优选地该澄清阶段由垂直直立的容器组成，该容器的形状通常是圆柱形，它是有一个内陶瓷耐火衬里，该衬里夹在一个密封的用水冷却的壳中。当熔融物料从溶化容器进入该容器时，它在该澄清容器中遇到降压。包裹在该熔体中的气体体积发生膨胀，产生了气泡。当气泡破灭后，它就进入保持在该澄清容器中的液化熔体中。澄清了的熔融物料从澄清容器的底部排放到接收室中并输送到浮法成型室中。
为了制造光学质量极好的玻璃，可以在该多阶段工艺中采用一种搅拌装置，用来将已经澄清的玻璃均化。如果需要，可以将搅拌装置和浮法成型室结合起来，从而使在该搅拌室中的玻璃停留在熔融金属层上。该熔融金属与在成型室中形成支承的熔融金属可以是连续的，它通常基本上由锡组成。
上面所说的多阶段工艺通常在氧化还原比为0.30或更高的情况下进行，但是通过增加玻璃配合料中的氧化性成分的含量可以使氧化还原比水平低于0.30。举例来说，可以加入氧化锰以降低氧化还原比，还可以通过调节燃烧器的气体/氧气比而控制氧化还原比。
在本发明全文中所给出的透光率数据均是以厚度为3.9毫米(0.154英寸)的玻璃为基础的。采用C.I.E.1931标准照明剂“A”在380-770纳米波长范围内以10纳米的间隔测量透光率(LTA)。在300-390纳米波长范围内以10纳米的间隔测量总太阳紫外线透射率(TSUV)。在800-2100纳米波长范围内以50纳米的间隔测量总太阳红外线透射率(TSIR)。总太阳能透射率(TSET)代表一个计算值，该计算值以在300-2100纳米波长范围内以50纳米的间隔测得的透光率数值为基础。所有的太阳透射率数据均采用Parry Moon气体质量2.0太阳数据计算。采用C.I.E.1931标准照明剂“C”、用2°观察器测量根据主波长和色纯度的玻璃颜色。
为了确定这些透光率数据，在波长范围[a,b]内对透光率数据进行积分。将该范围通过点{X0,X1,…Xn}分成n个长度为h的相等的子区间，其中Xi=a+(i×h)。在本发明中，采用矩形规则来计算透光率数据。采用一个插入值函数来近似每一个子区间中的被积函数f。该函数的积分的和提供了该积分的近似值：
根据该矩形规则，采用常数f(Xi)作为在[Xi-1,Xi]上的f(X)的近似值。这样就产生在[a,b]上的f(X)的阶梯函数近似值以及数值积分等式：
表1、2和3表示在3.9毫米(0.154英寸)参考厚度下的玻璃组合物的例子，这些例子体现了本发明的基本原则。在下表中仅列出了该例子中的着色剂部分，Fe2O3表示总铁，它包括以FeO形式存在的铁。
在表1和2中所给出的数据是以计算机模型为基础的，它根据该玻璃组合物产生理论光谱性质。表1中的组合物不用氧化镍作为着色剂，而表2中的组合物采用氧化镍作为着色剂。在表3中例31、32、33和34中所给出的数据是以实验室熔体为基础的。表3中其余的数据是以采用前面所说的多阶段熔化工艺而制得的实际玻璃为基础的。但是在一定的条件下，优选地在本发明中公开的玻璃可以采用前面所说的传统的上部烧成连续熔化法制造。
应该注意的是表1中的示范性组合物包括6-13PPM的Cr2O3和1PPM NiO，这两种物质均认为过程和/或残余物质，从而更好地反映该玻璃所期望的光谱性质。表2中的组合物包括相似的Cr2O3量。此外对表3中的实验熔体的分析的结果表明它具有低于3PPM的NiO和6-13PPM的Cr2O3。对表3中所述的实际制造的玻璃的分析结果表明它具有低于3PPM的NiO和5-8PPM的Cr2O3。
下面是实施例的有代表性的基础玻璃组合物：
实施例1-34 实施例35-39
SiO2 72.5％(重量) 72.0％(重量)
Na2O 13.6 13.5
CaO 8.8 8.8
MgO 3.8 3.8
Al2O3 0.12 0.59
应该了解，这个组成也可能有变化，特别是依具在玻璃组合物中实际存在的着色剂的量。
表1
Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10 Ex.11 Ex.12 Ex.13 Ex.14Fe2O3wt％0.935 0.820 1.100 0.820 0.820 0.820 0.710 1.000 0.710 0.600 0.710 0.710 0.450 0.600FeOwt％ 0.261 0.209 0.281 0.209 0209 0.209 0.181 0.255 0.181 0.153 0.181 0.181 0.115 0.153氧化还原比 0.279 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255CoO PPM 148 150 124 124 124 100 125 98 98 103 98 75 98 65Se PPM 23 20 20 24 16 20 14 14 17 15 11 14 14 9LTA 27.95 34.35 34.43 35.58 39.28 40.42 41.48 41.6 43.63 45.45 47.01 48.81 48.88 52.43TSIR 18.09 24.79 16.35 24.76 24.89 24.85 29.46 19.09 29.44 34.90 29.56 29.53 44.11 34.99TSUV 13.21 17.06 12.17 15.98 18.30 17.14 21.74 15.22 20.72 24.69 22.93 21.85 30.74 26.05TSET 23.58 30.30 24.95 30.32 32.38 32.32 36.16 29.62 36.51 40.63 38.41 38.60 47.34 43.48DW nm 500.3 489.5 551 572.4 495. 569.1 487.5 532.5 562.5 498.1 493.2 563 483.1 524.4Pe％ 0.97 2.66 3.67 4.84 2.39 5.41 4.17 2.51 2.7 0.90 3.02 3.88 1.27 1.13
注：Ex.-实施例
表2
Ex.15 Ex.16 Ex.17 Ex.18 Ex.19 Ex.20 Ex.21 Ex.22Fe2O3wt.％ 0.935 0.935 0.935 0.820 0.820 0.820 0.600 0.400FeOwt.％ 0.238 0.238 0.238 0.209 0.209 0.209 0.153 0.102氧化还原比 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255CoO PPM 170 160 150 124 124 124 110 102Se PPM 19 19 19 18 20 20 10 6NiO PPM 200 150 100 200 150 50 200 400LTA 24.48 26.21 28.06 33.86 34.07 36.25 41.74 42.21TSIR 20.36 20.25 20.55 24.44 24.51 24.72 34.40 46.29TSUV 13.51 13.56 13.62 17.49 16.96 17.05 26.55 36.94TSET 23.56 24.30 25.08 29.55 29.62 30.73 38.95 45.87DW nm 502.6 505.4 509.2 566.3 568.7 562.6 515.8 558.8Pe％ 1.62 1.40 1.22 6.16 6.2 3.27 1.29 3.55
表2(续)
Ex.23 Ex.24 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Ex.30Fe2O3wt％ 0.710 0.710 0.600 0.500 0.200 0.500 0.500 0.500FeO wt.％ 0.181 0.181 0.153 0.128 0.051 0.128 0.128 0.128氧化还原比 0.255 0.255 0.255 0.255 0.255 0.255 0.255 0.255CoO PPM 98 98 102 80 102 100 80 67Se PPM 14 14 12 4 0 8 2 7NiO PPM 100 50 100 400 500 200 400 100LTA 42.58 43.92 44.50 45.10 45.34 45.52 46.23 51.89TSIR 29∶25 29.38 36.67 39.69 63.20 40.24 39.74 40.58TSUV 21.68 21.74 25.84 33.32 55.13 31.41 34.46 30.90TSET 36.03 36.72 40.17 43.21 56.99 43.91 43.86 46.55DW nm 558.9 546.2 513.6 561.3 513.2 505.5 553.4 528.1Pe％ 3.37 1.91 .97 6.00 1.24 1.34 4.54 1.21
注：Ex.-实施例
表3
Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
31 32 33 34 35 36 37 38 39Fe2O3wt％ 0.935 0.930 0.818 0.820 0.822 0.811 0.772 0.720 0.657FeO wt.％ 0.261 0.257 0.245 0.257 0.216 0.212 0.198 0.185 0.160氧化还原比 0.279 0.276 0.300 0.313 0.263 0.261 0.257 0.257 0.244CoO PPM 128 120 126 124 104 101 90 75 62Se PPM 19 19 18 21 16 17 15 12 11LTA 31.20 31.95 32.08 35.83 36.15 36.57 41.05 46.30 51.85TSIR 18.07 18.40 19.25 18.34 25.12 26.01 28.34 29.32 32.62TSUV 17.35 16.59 22.81 24.15 21.55 21.52 24.08 27.97 31.75TSET 25.17 25.52 26.75 27.46 31.70 32.26 35.42 38.27 42.43DW nm 496.3 515.6 488.8 497.6 486.4 489.5 500.8 496.9 510.8Pe 1.72 1.05 2.79 1.59 2.62 1.41 0.62 1.05 0.65
注：Ex.-实施例
参考表1、2和3，本发明使用标准的钠钙硅玻璃作为基础组合物和铁、钴、硒和/或镍作为色剂提供了一种中性灰色玻璃。如同主波长(DW)和色纯度(Pe)表明的，不是所有实施例都是同样的灰色。在本发明中，优选的玻璃是中性灰色玻璃，其特征在于主波长在480-580nm范围内，优选为485-540nm，而色纯度不高于8％，优选不高于3％。
本发明中，用于制造厚度为3.9mm时的LTA在20％-50％范围内的中性灰色玻璃的着色剂包括0.15-1.2wt％Fe2O3(总铁)，不超过0.30％的FeO,60-180ppm CoO,0-30ppm Se和0-550ppmNiO，优选包括0.20-1.1wt％Fe2O3,0.05-0.29wt％FeO、62-170ppm CoO,0-24ppm Se和0-500ppm NiO。
本发明玻璃的氧化还原比保持在0.20-0.30，优选在0.24-0.28之间，这是用于传统的上部烧成熔化工艺的典型操作范围。通过这里公开的方法可以获得更高的氧化还原比，但优选避免使用更高的还原氧化比，以防止在熔化时硒的过度蒸发。
用浮法工艺制造的典型玻璃板的厚度为约1mm-10mm。对于车辆窗用玻璃的应用，优选玻璃板的厚度为1.8-6mm。
如果需要的话，可在本发明的玻璃组合物中添加紫外线辐射吸收材料以改进它的太阳性能。虽然本发明没有限制，但可以使用总量不超过2.0wt％的氧化铈、氧化钒、氧化钛和氧化钼或它们的组合作为UV吸收剂以降低玻璃的TSUV。在本发明的一个最佳实施方案，优选用TiO2作为UV吸收剂并且可以加入占玻璃组合物的0.1-1.0wt％的量，更优选加入0.2-0.5wt％的量。
本领域熟练技术人员在不背离后面权利要求书中限定的本发明范围的前提下也可以对本发明进行其出一些变化。
Claims (18)
1．一种中性灰色玻璃组合物，其基础玻璃部分包括：
SiO2 66至75重量％
Na2O 10至20重量％
CaO 5至15重量％
MgO 0至5重量％
Al2O3 0至5重量％
K2O 0至5重量％
而其着色剂部分基本上由以下物质组成：
Fe2O3(总铁) 0.820至0.935重量％
FeO 不超过0.30重量％
CoO 124至180ppm
Se 16至29ppm
该玻璃在厚度为3.9mm时，透光性为20至39.28％。
2．根据权利要求1的组合物，其中Fe2O3浓度为0.820至0.935重量％，FeO浓度为0.181至0.285重量％，CoO浓度为124至150ppm，而Se浓度为16至24ppm。
3．如权利要求1的组合物，其中玻璃的颜色特征为在厚度为3.9mm时主波长在480至580纳米范围，色纯度不高于8％。
4．如权利要求3的组合物，其中玻璃的颜色特征为，主波长在485-540纳米范围内，色纯度不高于3％。
5．如权利要求1的组合物，它还包括附加的紫外线吸收材料。
6．如权利要求5的组合物，其中所说的紫外线吸收材料是选自铈、钒、钛和钼以及它们的组合的材料的氧化物，其数量不超过玻璃组合物的2.0重量％。
7．如权利要求6的组合物，其中所说的紫外线吸收材料包括TiO2，其含量为0.1-1.O重量％。
8．如权利要求7的组合物，其中所说的TiO2含量为0.2-0.5重量％。
9．一种由权利要求1的玻璃组合物制成的玻璃板。
10．如权利要求9要求的玻璃板，其中玻璃板厚度为3-6mm。
11．如权利要求9要求的玻璃板，其中厚度为3.9mm时玻璃板的颜色特征为：主波长在480-580纳米范围内，并且色纯度不高于8％。
12．如权利要求11的玻璃板，其中玻璃的颜色特征为：主波长在485-540纳米范围内并且色纯度不高于3％。
13．一种中性灰色玻璃组合物，其基础玻璃部分包括：
SiO2 66至75重量％
Na2O 10至20重量％
CaO 5至15重量％
MgO 0至5重量％
Al2O3 0至5重量％
K2O 0至5重量％
而着色剂部分基本上由以下物质组成：
Fe2O3(总铁) 0.820至0.935重量％
FeO 0.102-0.238重量％
CoO 98至170ppm
Se 6至20ppm
NiO 50至400ppm
该玻璃在厚度3.9mm下的透光性为20至44.5％。
14．根据权利要求13的组合物，其中FeO浓度为0.181至0.238重量％，Se浓度为14至20ppm。
15．根据权利要求13的组合物，还包括附加的紫外线吸收材料。
16．根据权利要求15的组合物，其中所述的紫外线吸收材料选自铈、钒、钛和钼以及它们的组合的物质的氧化物，其量不超过玻璃组合物的2.0重量％。
17．根据权利要求16的组合物，其中所述的紫外线吸收材料包括其量为0.1至1.0重量％的TiO2。
18．根据权利要求17的组合物，其中TiO2含量为0.2至0.5重量％。
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| AU666829B2 (en) * | 1993-11-16 | 1996-02-22 | Ppg Industries Ohio, Inc. | Bronze glass composition |
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| US11351756B2 (en) | 2017-12-15 | 2022-06-07 | Corning Incorporated | Laminate glass ceramic articles with UV-and NIR-blocking characteristics and methods of making the same |
| KR102576995B1 (ko) | 2018-07-02 | 2023-09-12 | 삼성디스플레이 주식회사 | 디스플레이 장치 및 그 제조방법 |
| CN109734310B (zh) * | 2019-03-04 | 2021-12-03 | 南通市国光光学玻璃有限公司 | 一种可见光深截止的高透光学玻璃 |
| KR20210095265A (ko) | 2020-01-22 | 2021-08-02 | 삼성디스플레이 주식회사 | 표시 장치 |
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- 1994-11-10 DE DE69417348T patent/DE69417348T3/de not_active Expired - Lifetime
- 1994-11-10 EP EP94117722A patent/EP0653388B9/en not_active Expired - Lifetime
- 1994-11-10 AT AT94117722T patent/ATE178035T1/de not_active IP Right Cessation
- 1994-11-10 DK DK94117722T patent/DK0653388T4/da active
- 1994-11-10 ES ES94117722T patent/ES2133463T5/es not_active Expired - Lifetime
- 1994-11-14 BR BR9404457A patent/BR9404457A/pt not_active IP Right Cessation
- 1994-11-15 CA CA002135820A patent/CA2135820C/en not_active Expired - Lifetime
- 1994-11-15 JP JP6280716A patent/JPH0867526A/ja active Pending
- 1994-11-15 KR KR1019940029906A patent/KR0123879B1/ko not_active IP Right Cessation
- 1994-11-15 CN CN94118331A patent/CN1043217C/zh not_active Expired - Lifetime
- 1994-12-09 TW TW083111485A patent/TW272180B/zh not_active IP Right Cessation
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1995
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Also Published As
| Publication number | Publication date |
|---|---|
| ES2133463T3 (es) | 1999-09-16 |
| US20010025002A1 (en) | 2001-09-27 |
| DK0653388T4 (da) | 2004-02-02 |
| AU7767494A (en) | 1995-06-08 |
| CA2135820C (en) | 2000-01-04 |
| EP0653388B9 (en) | 2004-11-10 |
| KR0123879B1 (ko) | 1997-11-24 |
| JP3155493B2 (ja) | 2001-04-09 |
| EP0653388A1 (en) | 1995-05-17 |
| JPH0867526A (ja) | 1996-03-12 |
| TW272180B (zh) | 1996-03-11 |
| JPH1067535A (ja) | 1998-03-10 |
| DK0653388T3 (da) | 1999-10-25 |
| DE69417348D1 (de) | 1999-04-29 |
| EP0653388B2 (en) | 2004-01-02 |
| EP0653388B1 (en) | 1999-03-24 |
| ATE178035T1 (de) | 1999-04-15 |
| ES2133463T5 (es) | 2004-09-01 |
| DE69417348T2 (de) | 1999-10-07 |
| AU666831B2 (en) | 1996-02-22 |
| CA2135820A1 (en) | 1995-05-17 |
| NZ264880A (en) | 1995-09-26 |
| BR9404457A (pt) | 1995-07-11 |
| US6274523B1 (en) | 2001-08-14 |
| DE69417348T3 (de) | 2004-06-24 |
| KR950014012A (ko) | 1995-06-15 |
| CN1108625A (zh) | 1995-09-20 |
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| SE01 | Entry into force of request for substantive examination | ||
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| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent of invention or patent application | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: PATENTEE; FROM: PPG INDUSTRIES INC. TO: PPG IND OHIO INC. |
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| CP03 | Change of name, title or address |
Address after: American Ohio Patentee after: PPG Industries, Inc. Address before: American Pennsylvania Patentee before: PPG Industries Inc. |
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| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 19950920 Assignee: Hainan AVIC Special Glass Materials Co., Ltd. Assignor: PPG Industries, Inc. Contract record no.: 2010990000109 Denomination of invention: Grey glass composition for production of windows Granted publication date: 19990505 License type: Common License Record date: 20100304 |
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| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20141115 Expiration termination date: 20141115 Granted publication date: 19990505 |