CN1135744A - 玻璃组合物 - Google Patents
玻璃组合物 Download PDFInfo
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- CN1135744A CN1135744A CN95190949A CN95190949A CN1135744A CN 1135744 A CN1135744 A CN 1135744A CN 95190949 A CN95190949 A CN 95190949A CN 95190949 A CN95190949 A CN 95190949A CN 1135744 A CN1135744 A CN 1135744A
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- glass
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- soda lime
- iron
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- 239000011521 glass Substances 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052742 iron Inorganic materials 0.000 claims abstract description 40
- 230000005540 biological transmission Effects 0.000 claims abstract description 30
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 15
- 238000002834 transmittance Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000006132 parent glass Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000005329 float glass Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- -1 cobalt oxide compound Chemical class 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract 1
- 239000006066 glass batch Substances 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 10
- 229910052711 selenium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000005357 flat glass Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000006124 Pilkington process Methods 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 230000002650 habitual effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
- C03C1/10—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce uniformly-coloured transparent products
-
- 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
-
- 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
Abstract
一种吸收红外线和紫外线的中性色调的钠—钙—硅玻璃,其含有0.3%至0.7%(重量)的表示为Fe2O3的总铁量,也含有适量的Se、Co3O4和二价铁,其含量以保持二价铁与总铁的比值在21在34之间,也可将NiO和TiO2加到这种玻璃中。标称4mm厚的产品玻璃具有至少70%的可见光透射率,它的直射阳光热透射率比可见光透射至少低12个百分点。玻璃中的铁最好由玻璃配料中方铁矿提供。
Description
发明背景
本发明涉及使用在玻璃窗上的能吸收红外线(IR)和紫外线(UV)的钠-钙-硅玻璃(Soda-Lime-silica glass)组合物。更具体的是,本发明主要涉及由这种玻璃制造的中性色调的玻璃窗,但是,不排除用在象汽车那样的交通车辆上。
作为交通车辆中使用的特种玻璃已有了发展,它们具有低水平的直射阳光热透射率(DSHT)和紫外线透射率(UVT)。用这些玻璃的目的在于减少在交通车辆内因阳光照射而产生的过热而引起的问题,防止汽车的内部设备因紫外线照射而老化。具有好的红外线吸收性质的玻璃通常是由还原存在于玻璃中的铁到亚铁(二价)状态或者通过加入铜而制造出来的。这种材料给玻璃以一种兰色。为了获得好的紫外线吸收性质而添加的材料是Fe3+,Ce,Ti或V。为了提供所要求的吸收水平,加入这种材料的量倾向于使玻璃色彩为黄色。因此,在相同玻璃中如果既要有好的紫外线吸收性质又要有好的红外线吸收性质的话,这种玻璃的色彩几乎都是绿色或者蓝色。当玻璃的色彩用CIELAB系统测定时,发现4mm厚的具有大于60%的光透射率的商业用玻璃不是非常绿(-a*>8)就是非常兰(-b*>7)的,但从审美的观点来讲,它们没有一个是目前所要求的。
已经试图制造灰色的或者青铜色的、防止红外线和紫外线辐射性能好的交通车辆玻璃窗,但是这种玻璃仍然趋向于一种带浅绿的黄色调。
我们已经确定了一系列具有中性色调可见光透射率(照明体A)至少在70%以上的玻璃的技术要求,使在CIELAB系统里,玻璃具有范围在a*从-7到+1,b*从-5到+7.5的色彩座标。下文所用的名词“中性色调”就是常用来描述具有这种色彩座标的玻璃的。
我们已进一步确定了具有中性色调的玻璃的技术要求。它至少有70%的可见光透射率(在4mm厚时),并且它还具有直射阳光热透射率至少小于可见光透射率12个百分点(优选为15个百分点,最好是20个百分点)。基本上,已经知道玻璃的确具有低的直射阳光热透射率,但是,几乎所有这些玻璃都有一个低的光透射率,这就使这些玻璃在交通车辆上的应用受到限制。我们预料,能满足以上确定的技术要求的玻璃一定能更加普遍地使用在交通车辆中,这是由于它具有较高的光透射率而且有较低的直射阳光热透射率,一定能保持汽车内部冷却而不管其较高的光透射性。
此外,我们相信,如果玻璃有少于55%,理想的是少于50%的紫外线透射率,则正是所要求的,因为我们感到这样低的透射率将使紫外线辐射对塑料物质和纤维的有害影响减少到最小程度,尤其是在汽车里。
就着色玻璃而言,是一种只要有比较小的变化就能在色调上产生较大的变化的玻璃。现有专利公开的宽范围可包括许多可能性,但这只是一些可用来确定特定色调是怎样同可能获得红外线和紫外线的特定吸收范围相关联的具体实例的解说。
我们的发明就是基于那种令人惊异的发现,就是比较少量的某种着色剂的掺入补偿了绿色,这些绿色起因于吸收红外线和紫外线辐射的组分的存在。发明概要
按照本发明,提供了一种吸收红外线和紫外线的中性色调厚度为4mm的(如本文中所定义的)钠钙硅玻璃,其可见光透射率至少在70%,直射阳光热透射低于可见光透射率至少12个百分点,紫外线透射率不大于55%,主波长小于560nm,色彩纯度不大于6,优选不大于5,最好不大于3。直射阳光热透射率最优选至少低于可见光透射率20个百分点。组合物包括一种钠-钙-硅基础玻璃和以Fe2O3表示,其含量在0.3%~0.7%(重量)之间的总铁。这种被着色成中性色彩的玻璃,是用掺杂方法制成的,杂质是0.5~10ppm的Se,大约3~25ppm的Co3O4和二价铁,其含量为应使得二价铁对总铁量的比值在21~34的范围内,最好是在25~31之间(即作为亚铁(Fe2+)的总铁百分比为21%~34%,最好是25%~31%*)。NiO和TiO2也可加入玻璃中,其用量范围是0~50ppm NiO和0~1.5%(重量)的TiO2。因此,已经确定,NiO和TiO2的量,只要在上述范围内就能在色彩纯度上和紫外线吸收方面分别产生有利的影响,各自不会对我们新型玻璃的特色和高的优越性产生不利的影响。
为了本说明书和权利要求的目的,对于可见光透射的参照是使用CIE(相干红外能量)照明体A测量的光透射;UVT或紫外线辐射透射是一个积分项,代表着在透射光与300-400nm波长的关系曲线下的区域面积,对于直射阳光热透射(DSHT)的参照是依据太阳光热透射的积分关系,它是在波长范围为350~2100nm内根据相对的太阳光谱分布Parry Moon对气团2的积
注*:众所周知:在玻璃中铁的含量通常存在着两种形态,即Fe2O3(三价铁的)和FeO(二价铁的)。作为惯例,存在于玻璃中的总铁在本文中表示为Fe2O3,而不管其实际存在的形态。分。
为制造根据本发明的玻璃产品,适当的配料是用惯用的玻璃配料混合装置混合而成的,配料包括砂子,石灰,白云石,苏打粉,盐饼或石膏,硝石,氧化铁,碳,硒和氧化钴(Co3O4)。最终在组合物中还要求有TiO2和/或NiO,如二氧化钛的钛化合物和如氧化镍的镍化合物均可包含在配料里。在这方面,按照这个发明的重要的实施方案,惊人地发现应用方铁矿作为铁的来源是特别有利的,它可提供至少一部分或者最好是全部的Fe2O3,基本上就不再需要碳了。因此,在中性色调玻璃中,例如,灰色和青铜色玻璃,碳是一种非常有害的元素,但需要它是因为在应用铁丹作为配料的铁来源时用于增加玻璃的二价铁值。使用方铁矿作为铁源代替铁丹,大大地增加了玻璃的二价铁值。应用有较高的天然二价铁值的原料可更好地控制玻璃中较高的二价铁值,就像本发明的中性色调玻璃那样。
配料可方便地在一种惯用的玻璃制造炉里一起熔化,这样就形成了一种吸收红外线能和紫外线辐射的中性色调的玻璃组合物,此组合物在浮法玻璃制造中可被连续浇铸到熔融的金属熔池上。
适合应用于本发明的钠-钙-硅平板玻璃组合物典型地具有以下重量百分组成:
SiO2 65~80%
Na2O 10~20
CaO 5~15
MgO 0~10
Al2O3 0~5
K2O 0~5
BaO 0~5
B2O3 0~5
其它次要的成分,包括熔融和精炼助剂像SO3,也会出现在玻璃组合物中。上述的本发明着色组分被加进这种基础玻璃中。除了铁、钴和硒以及任选的镍和钛以及任何作为杂质的痕量氧化物以外,玻璃基本上是无着色剂的。因此,本发明的玻璃可在惯用的槽形熔炉里熔化和精制,并且采用浮法形成各种厚度的平板玻璃片,此浮法是使熔融的玻璃被支托在熔融金属池上,通常使用锡,这样玻璃就呈条带形并被冷却。
本发明的玻璃组合物特别适用于制造为汽车和建筑玻璃窗所用的能吸收红外线能量和紫外线辐射的玻璃。因此,这种组合物的玻璃板可以被加热强固或回火处理,或者交替地退火韧化处理和通过插入一种例如由聚乙烯醇缩丁醛组成的透明树脂层,一起层压用作为挡风玻璃。一般来说,作为挡风玻璃用的玻璃片厚度范围大约是1.7mm,到大约2.5mm,而这些回火的、用作边窗或后窗的玻璃厚度约在3mm到大约5mm的范围。
除非另作说明,此处和附加的权利要求中所用的术语百分比(%)都是指重量百分比。用波长色散X-射线荧光分析法来测定TiO2的重量百分比和表示为Fe2O3的总铁重量百分比。总铁的百分比减少是首先使用分光光度计测量一个样品在1060毫微米波长时的辐射透射测定的。该1060nm透射值而后用来计算光密度,所用公式如下:(T0=100 减去从反射=92时估计的损失;T=1060nm时的透射)。
三种主要着色剂组分的每个组份的浓度,都依赖于玻璃所要求的光学性质,并且相互有关联。加入铁后,典型的如Fe2O3,会部分地还原成FeO。配料中铁的总量是严格的,必须等于0.3%到大约0.7%(重量),用Fe2O3表示。同样,还原的程度也是严格的,必须等于21%-34%。假如被还原的铁量高于临界量,或者更高的总铁量被应用的话,玻璃将变得太暗,并且照明体A的可见光透射率将落到大约70%以下。此外,由于增加了FeO的量后阻碍热穿透到熔融物的内部,将增加玻璃配料熔融方法的困难。如果铁的还原少于临界量,或者,如果应用较低的总铁量,那么,对于一个所要求厚度的玻璃来说,直射阳光热透射率可以升到一个不能接受的水平,即,大约在58%以上。
大约3~25ppm的氧化钴被加进去,典型的为Co3O4,以及加入大约0.5~约10ppm硒。适当的硒和钴含量对玻璃提供了一种审美乐趣和中性色调,使玻璃稍微有点灰色。优选的组合物包括一种钠-钙-硅基础玻璃和着色剂,基本上含0.45~0.65的总铁(以Fe2O3表示),二价铁对总铁的比例为25~31,1~5ppm的Se,8~20ppm的Co3O4,0~35ppm的NiO和0~1的重量百分比的TiO2。
下面的实例说明根据本发明准备制成玻璃制品或玻璃窗,像汽车挡风玻璃那样的玻璃组合物。这种组合物可吸收红外线和紫外线,并且具有一个照明体A的可见光透射率至少大约是70%,以及直射太阳光热透射率至少要小于可见光透射率12个百分点。
除了只用作比较的实例1和11之外,所有实例用于说明但并不限制本发明。在这些实例中,所有份数和百分比均以重量计,以及:
(a)Fe2O3,FeO,和TiO2是以百分比表示;Se,Co3O4和NiO是用ppm来表示;
(b)总铁被表示为好象所有存在的铁都是以氧化铁形态存在着;以及
(c)氧化亚铁(FeO)含量由以下公式计算
其中Fe2O3=在玻璃中用Fe2O3表示的总铁量的百分数,(143.7是2×FeO的分子量,159.7是Fe2O3的分子量)。
列于下表中的透射率数据全都是基于标称4mm厚的玻璃。
实例
表1
1 2 3 4 5表示为Fe2O3
0.5 0.55 0.55 0.31 0.61的总铁FeO 0.11 0.14 0.13 0.08 0.14表示为Fe2+的
25 29 27 27.2 26总铁的%Se 2 7 9 3 2Co3O4 10 10 19 20 12TiO2 1.6 0.33 0.34 - -NiO - - 15 - -光透射率LT 72 71 71 75 73直射太阳光热 53 50 51 63 51透射DSHT紫外线透 36 45 47 59 51射UVTa* -5.1 -4.8 -5.2 -2.0 -4.7b* 7.5 3.2 2.4 0.2 1.5\D 565 546 529 499 512纯度 6.9 2.4 1.7 0.8 1.3
表1(续)
6 7 8 9 10 11表示为Fe2O3
0.56 0.56 0.54 0.57 0.51 0.53的总铁FeO .13 0.14 0.13 0.16 0.12 0.09表示为Fe2+的
25 27 27 31 27 19总铁的%Se 2 1 1 <1 2 5Co3O4 5 13 24 10 l2 13TiO2 - - - - 1.0 -NiO 23 - 31 - - -光透射率LT 76 74 72 74 71 71直射太阳光热 54 52 53 50 52 57透射DSHT紫外线透 51 51 53 53 40 46射UVTa* -4.9 -5.3 -5.0 -6.2 -5.2 -1.9b* 1.9 0.3 -1.0 -0.8 5.5 4.1\D 518 498 499 494 560 569纯度 1.3 2.3 3.3 3.6 4.8 4.0
实例7的基础玻璃组合物与所有实例的组合物基本上相同,其组成如下:
组分 占总玻璃的重量百分比
SiO2 73.91
Na2O 14.04
CaO 7.86
MgO 3.47
SO3 0.20
Al2O3 0.16
K2O 0.039
实例7的配料混合物,除了着色剂以外,与其它所有实例的配料同样也相类似,为:
组分 重量份数
砂子 154
苏打粉 50
石膏 1
石灰 11
白云石 33
方铁矿 1.02
C3O3 0.0011
硒 0.0014
碳 0.027
本发明的优点在于这种组合物可以采用工业的制造方法,特别是用浮法制造成平板玻璃产品。由浮法制成的玻璃板的特征是,适量的氧化锡迁移到玻璃的至少一面的表面部分。典型的一块浮法玻璃具有SnO2的浓度至少为0.05%(重量),它存在于与锡接触的表面下最初的几微米处。典型的由浮法制得的玻璃其厚度大约从2毫米到10毫米。
多数浮法玻璃的另一个特点是存在痕量的熔融和精制助剂,像硫,分析为在玻璃中以SO3存在,或者氟或氯。少量的这些熔融和精制助剂(通常少于0.3%(重量))可以存在于本发明的玻璃组合物中而不会影响其性质。
本发明的详细说明已参照具体的实例进行描述,但是应该明白,对那些本技术领域的技术人员已知的变化和改进,可以在不脱离以下权利要求所确定的本发明的范围内采用。
Claims (12)
1.一种吸收红外线和紫外线的中性色调的钠-钙-硅玻璃,它具有标称厚度4mm,可见光透射率至少为70%,直射阳光热透射率低于可见光透射率至少12个百分点,主波长不大于560nm以及色彩纯度不大于6%,上述的玻璃以重量为基准包括的基本配料是,用Fe2O3表示的总铁含量大约是0.3%~0.7%,大约0.5~10ppm的Se,大约3~25ppm的Co3O4,0~50ppm的NiO和0~1.5%的TiO2,以及二价铁对总铁(以Fe2O3表示)的比值在21~34的范围内。
2.权利要求1的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述直射阳光热透射率低于可见光透射率至少15个百分点。
3.权利要求1的吸收红外线和紫外线的钠-钙-硅玻璃,具有少于55%的紫外线透射率。
4.权利要求3的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述紫外线辐射透过率少于50%。
5.一种中性色调的吸收红外线和紫外线的钠-钙-硅玻璃,其具有标称厚度4mm,可见光透过率至少有70%,直射阳光热透射率低于可见光透射率至少15个百分点,主波长不大于560nm,色彩纯度不大于6%,上述的玻璃以重量为基准包括基本的配料是,用Fe2O3表示的总铁含量大约是0.45%~0.65%,大约1~5ppm的Se,大约8~20ppm的Co3O4,0~35ppm的NiO和0~1%TiO2,以及二价铁对总铁(用Fe2O3表示)之比值为25~31的范围内。
6.权利要求5的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述直射阳光热透射率低于可见光透射率至少20个百分点。
7.权利要求5的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述色彩纯度不大于5%。
8.权利要求5的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述色彩纯度不大于3%。
9.权利要求5的吸收红外线和紫外线的钠-钙-硅玻璃,具有紫外线辐射的透过率小于55%。
10.权利要求9的吸收红外线和紫外线的钠-钙-硅玻璃,其中所述紫外线辐射的透过率小于50%。
11.一种中性色调的吸收红外线和紫外线的钠-钙-硅玻璃,具有的基础玻璃组成按重量百分比为:
SiO2 65~80
Na2O 10~20
CaO 5~15
MgO 0~10
Al2O3 0~5
K2O 0~15
BaO 0~5
B2O3 0~5
以及痕量的熔融和精制助剂,如果存在着色剂,主要由以下组分构成:
Fe2O3(总铁) 0.3~0.7重量百分比
Se 0.5~10ppm
Co3O4 3~25ppm
TiO2 0~1.5重量百分比;
NiO 0~50ppm;以及
FeO 其含量提供了二价铁对总铁之比是在
21~34的范围内,
此种玻璃在标称厚度为4mm时具有可见光透射率至少为70%,直射阳光热透射率低于可见光透射率至少12个百分点,主波长不大于560nm,以及色彩纯度不大于6%。
12.一种制造能吸收红外线和紫外线的、包含有铁和钴的氧化物以及二价铁对总铁(以Fe2O3表示)之比在21~34范围内的中性色调玻璃的方法,包括混合、加热和熔融钠-钙-硅浮法玻璃的配料混合物,此配料混合物包含砂子,苏打粉,白云石,石灰和选自盐饼和石膏的硫酸盐,其改进包括在上述配料中以方铁矿作为在产品玻璃中氧化铁的至少一部分来源。
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BE759862A (fr) * | 1969-12-11 | 1971-06-04 | Asahi Glass Co Ltd | Nouveau verre gris neutre |
GB1331492A (en) * | 1970-06-18 | 1973-09-26 | Pilkington Brothers Ltd | Coloured glasses |
US4190452A (en) * | 1974-12-03 | 1980-02-26 | Saint-Gobain Industries | Neutral bronze glazings |
LU83164A1 (fr) * | 1980-03-04 | 1981-06-05 | Bfg Glassgroup | Verre colore et son procede de fabrication |
US4792536A (en) * | 1987-06-29 | 1988-12-20 | Ppg Industries, Inc. | Transparent infrared absorbing glass and method of making |
US5023210A (en) * | 1989-11-03 | 1991-06-11 | Ppg Industries, Inc. | Neutral gray, low transmittance, nickel-free glass |
US5112778A (en) * | 1990-01-30 | 1992-05-12 | Libbey-Owens-Ford Co. | Batch composition for making infrared and ultraviolet radiation absorbing green glass |
KR100208922B1 (ko) * | 1991-02-08 | 1999-07-15 | 마쯔무라 미노루 | 차량용 창유리 |
EP0565882B1 (en) * | 1992-03-19 | 1997-06-04 | Central Glass Company, Limited | Neutral gray-colored infrared and ultraviolet radiation absorbing glass |
KR100206628B1 (ko) * | 1992-04-22 | 1999-07-01 | 마쯔무라 미노루 | 차량용 창유리 |
US5346867A (en) * | 1993-12-17 | 1994-09-13 | Ford Motor Company | Neutral gray absorbing glass comprising manganese oxide for selenium retention during processing |
-
1994
- 1994-08-03 US US08/285,652 patent/US5478783A/en not_active Expired - Lifetime
-
1995
- 1995-07-17 WO PCT/US1995/009149 patent/WO1996004212A1/en active IP Right Grant
- 1995-07-17 BR BR9506300A patent/BR9506300A/pt not_active IP Right Cessation
- 1995-07-17 EP EP95927301A patent/EP0721429B1/en not_active Expired - Lifetime
- 1995-07-17 AU AU31372/95A patent/AU699949B2/en not_active Ceased
- 1995-07-17 ES ES00250274T patent/ES2194674T3/es not_active Expired - Lifetime
- 1995-07-17 CN CN95190949A patent/CN1073052C/zh not_active Expired - Fee Related
- 1995-07-17 MX MX9601176A patent/MX9601176A/es unknown
- 1995-07-17 JP JP50655796A patent/JP3731896B2/ja not_active Expired - Fee Related
- 1995-07-17 KR KR1019960701708A patent/KR100360628B1/ko not_active IP Right Cessation
- 1995-07-17 DE DE69520871T patent/DE69520871T2/de not_active Expired - Fee Related
- 1995-07-17 EP EP00250274A patent/EP1067098B1/en not_active Expired - Lifetime
- 1995-07-17 CA CA002172133A patent/CA2172133C/en not_active Expired - Fee Related
- 1995-07-17 DE DE69530330T patent/DE69530330T2/de not_active Expired - Fee Related
- 1995-07-25 TW TW084107715A patent/TW367312B/zh not_active IP Right Cessation
- 1995-07-31 ZA ZA956370A patent/ZA956370B/xx unknown
- 1995-08-01 TR TR95/00930A patent/TR199500930A2/xx unknown
-
1997
- 1997-10-21 US US08/955,106 patent/US5910460A/en not_active Expired - Lifetime
-
1998
- 1998-11-04 US US09/185,805 patent/US5928974A/en not_active Expired - Lifetime
-
2004
- 2004-08-09 JP JP2004232159A patent/JP3769571B2/ja not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100473619C (zh) * | 2000-04-04 | 2009-04-01 | 旭硝子欧洲平板玻璃股份有限公司 | 高光透射率的着色钠钙玻璃 |
CN1898169B (zh) * | 2003-12-26 | 2010-08-11 | 日本板硝子株式会社 | 近红外线吸收绿色玻璃组合物及使用该组合物的夹层玻璃 |
CN106460451A (zh) * | 2014-06-03 | 2017-02-22 | 皮尔金顿集团有限公司 | 耐火玻璃屏 |
CN106460451B (zh) * | 2014-06-03 | 2020-04-21 | 皮尔金顿集团有限公司 | 耐火玻璃屏 |
CN106186670A (zh) * | 2016-08-15 | 2016-12-07 | 安徽恒春玻璃股份有限公司 | 一种中空玻璃 |
CN110291053A (zh) * | 2016-12-19 | 2019-09-27 | 旭硝子欧洲玻璃公司 | 具有消色差且发光的边缘的玻璃板 |
CN114423718A (zh) * | 2019-10-07 | 2022-04-29 | 日本电气硝子株式会社 | 紫外线透射玻璃 |
Also Published As
Publication number | Publication date |
---|---|
JP3731896B2 (ja) | 2006-01-05 |
US5910460A (en) | 1999-06-08 |
TR199500930A2 (tr) | 1996-10-21 |
AU699949B2 (en) | 1998-12-17 |
KR100360628B1 (ko) | 2003-01-25 |
EP0721429A4 (en) | 1997-02-19 |
EP0721429A1 (en) | 1996-07-17 |
WO1996004212A1 (en) | 1996-02-15 |
JPH09505797A (ja) | 1997-06-10 |
ES2194674T3 (es) | 2003-12-01 |
DE69530330D1 (de) | 2003-05-15 |
JP2005047801A (ja) | 2005-02-24 |
EP1067098B1 (en) | 2003-04-09 |
EP0721429B1 (en) | 2001-05-09 |
DE69530330T2 (de) | 2004-03-04 |
CA2172133A1 (en) | 1996-02-15 |
BR9506300A (pt) | 1997-08-05 |
JP3769571B2 (ja) | 2006-04-26 |
MX9601176A (es) | 1997-06-28 |
US5478783A (en) | 1995-12-26 |
EP1067098A1 (en) | 2001-01-10 |
US5928974A (en) | 1999-07-27 |
CN1073052C (zh) | 2001-10-17 |
AU3137295A (en) | 1996-03-04 |
DE69520871D1 (de) | 2001-06-13 |
CA2172133C (en) | 2008-01-22 |
ZA956370B (en) | 1996-03-14 |
DE69520871T2 (de) | 2001-11-08 |
TW367312B (en) | 1999-08-21 |
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