CN1039404C - 含有能在加工过程中保持硒的氧化锰的中性灰色吸收玻璃 - Google Patents
含有能在加工过程中保持硒的氧化锰的中性灰色吸收玻璃 Download PDFInfo
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- 230000007935 neutral effect Effects 0.000 title claims abstract description 33
- 239000011669 selenium Substances 0.000 title claims description 61
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims description 55
- 229910052711 selenium Inorganic materials 0.000 title claims description 55
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims description 47
- 238000004519 manufacturing process Methods 0.000 title description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002834 transmittance Methods 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 36
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 27
- 229940001516 sodium nitrate Drugs 0.000 claims description 18
- 235000010344 sodium nitrate Nutrition 0.000 claims description 18
- 239000004317 sodium nitrate Substances 0.000 claims description 18
- 230000005284 excitation Effects 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
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- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 239000011734 sodium Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
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- 230000002829 reductive effect Effects 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 230000000295 complement effect Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-O hydridodioxygen(1+) Chemical compound [OH+]=O MYMOFIZGZYHOMD-UHFFFAOYSA-O 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 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
- URMHSIWBWVSJBI-UHFFFAOYSA-N nickel sulfurous acid Chemical compound [Ni].S(O)(O)=O URMHSIWBWVSJBI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 238000001429 visible spectrum Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- 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
-
- 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
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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)
Abstract
一种中性灰色玻璃组合物,该组合物在4mm的控制厚度下使用照明剂A时的光透射率为10.0%-55.0%,紫外透射率小于25.0%,红外透射率小于50.0%,它用基本上由0.90-1.90wt%以Fe2O3计的总的氧化铁;0.002-0.025wt%的以Co计的钴;0.0010-0.0060wt%以Se计的硒;0.10-1.0wt%的以MnO2计的氧化锰;以及0-1.0wt%的以TiO2计的氧化钛组成的着色剂所生产。具有这种组成的平板玻璃特别适于用作卡车和汽车的隐蔽用的玻璃或遮阳产品。
Description
发明背景
本发明涉及一种能吸热的中性灰色玻璃组合物。具体地说,它由钠钙硅玻璃(soda-lime-silica glass)组成,其着色组份包括氧化铁、钴、硒、二氧化锰,此外还可选择性地含有二氧化钛。
具有中性灰色以及低红外透射率、低总太阳能透射比的玻璃能减少外壳内部获得的热量,该种玻璃在汽车领域内是人们所非常希望的。选择中性灰色玻璃是为了与宽范围的汽车涂料颜色相一致。为使之在汽车领域内特别有用,玻璃组合物应当与平板(flat)玻璃生产方法相匹配。具有这些性质的玻璃组合物是非常必要的,特别是在汽车的隐蔽和防晒应用上是必要的。
某些吸热玻璃组合物含有作为基本着色组份的硒。如Jones的US4,873,206公开了一种灰色玻璃组合物,它含有的着色剂仅有铁、钴和硒。硒是一种熔点相对低的组份,其熔点是217℃,沸点是685℃,在玻璃的熔化和加工过程中,经常有85%或更多的硒从配料中挥发了。硒是一种十分昂贵的材料,因此其在玻璃熔化中的挥发应尽量少。为了在玻璃产品中保留更多的硒,尽管玻璃生产商经常在玻璃组合物中使用硝酸钠和钾,还是会发生大量的挥发。
通过向灰色玻璃组合物中加入硒的同时掺入氧化锰,本发明克服了与硒的挥发有关的问题。我们令人意外地发现向含硒的玻璃组合物中掺入氧化锰有助于硒在熔化过程中的保留。
此外,与Jones在上述专利中的建议相反,在本发明的组合物中含有氧化铁和氧化锰不会导致日晒作用(solarization)的增加。日晒作用是当玻璃在太阳光下暴露于紫外线时,在玻璃中发生反应的结果。这些反应的一种是Fe+3转变为Fe+2。日晒作用使得铁从氧化态变为还原态,从而引起玻璃产品中所不希望的颜色变化。Milos B.Volf就这一问题在Chemical Approach to Glass(Elsevier Science PublishCo.,Inc.,1984)的343页上已有过讨论,“锰作为脱色剂具有产生日晒作用和对炉内温度敏感的缺点。”
在过去,灰色吸热玻璃通常含有氧化镍作为活性着色剂。然而,我们知道镍化合物能与钠钙玻璃中的其它物质反应,在玻璃中生成亚硫酸镍“石头”。这些石头通常很小,因此检测不出来,但在玻璃在回火时会产生不能接受的高破裂率。Krumwiede等人在US5,023,210中公开了一种结合使用氧化铬与氧化铁、氧化钴和硒得到暗灰色无镍玻璃的方法。该玻璃中不含MnO2。发明概述
本发明是一种硒保留率得到了改进的吸热中性灰色钠钙玻璃组合物。该组合物的范围最宽的方案包括68-75%的SiO2,10-18%Na2O,5-15%CaO,0-10%MgO,0-5%Al2O3,以及0-5%K2O,其中CaO+MgO为6-15%,Na2O+K2O为10-20%,必要时,有痕量的熔化和澄清助剂,和基本上由0.9-1.9wt.%以Fe2O3计的总的氧化铁;0.002-0.025wt.%的以Co计的钴;0.0010-0.006wt.%以Se计的硒;0.10-1.0wt.%的以MnO2计的氧化锰;以及0.0-1.0wt.%的以TiO2计的氧化钛组成的着色剂。
按本发明方案制备的玻璃产品在4mm厚度下具有如下光谱性质:使用照明剂A(LTA)时,光透射率为10.0-55%,紫外透射率小于25.0%,红外透射率小于50.0%。组合物的主波长为470-590纳米。随着着色剂量的增加,%透射率下降。同样,对于给定的玻璃组合物玻璃的厚度增加,较厚的玻璃的透射率也下降。
我们令人意外地发现:在配料中引入氧化锰比引入硝酸盐能增加硒在玻璃产品中的保留率。氧化锰的主要作用虽然是为了提高硒的保留率,但氧化锰在与硒组份相同的可见光谱区域上,也有一些吸收,因此引入氧化锰进一步增加了灰度。由于氧化锰能用来提供灰颜色,所以在组合物中需要的昂贵的硒的量较少。本发明的玻璃组合物具有灰的颜色,但不必加入镍。发明详述
用在汽车和建筑业的钠钙平板玻璃通常是用平板玻璃法生产的,这种玻璃的特征在于列于表1的基本组成,组份的量是以占总的玻璃组合物的重量百分比为基础的。
表1
氧化物组份 | 重量% |
SiO2 | 68-75 |
Al2O3 | 0-5 |
CaO | 5-15 |
MgO | 0-10 |
Na2O | 10-18 |
K2O | 0-5 |
本发明的中性灰色玻璃使用了这一基本钠钙玻璃组成,此外,CaO+MgO为6-15%,Na2O+K2O为10-20%。优选SO3的量为0.10-0.30wt.%,进一步优选0.14-0.25wt.%。另外中性灰色玻璃组合物主要含有下列着色组份:氧化铁、氧化钴、硒、氧化锰以及可选的二氧化钛。
以Fe2O3计,在本发明组合物中氧化铁的量为0.9-1.9wt.%。在这里所有重量百分数都是以本发明玻璃组合物的总重量为基础的。这些组份一般是以氧化物的形式添加到配料组份中,如Fe2O3。掺入组合物中的氧化铁降低玻璃产品对紫外和红外的透射率。特别地,在玻璃组合物中,氧化铁具有两种作用:(1)氧化型的氧化铁(Fe2O3)吸收光谱中的紫外部分,提供了低的紫外透射率,(2)还原型氧化铁(FeO)吸收光谱中的红外部分,使得玻璃产品具有低的红外透射率。当玻璃产品是用在汽车上时,这两种作用都是特别有价值的。当热量被玻璃吸收后,空调的负荷就明显降低了,在汽车中的总热量较少。
钴也通常以氧化物的形式添加到配料中,在本发明组合物中作为着色剂,以Co计,其量为0.002-0.025wt.%,钴的作用是吸收光谱中580-680纳米的可见光部分。硒通常是以金属的形式添加到配料中,作为着色剂,以Se计,其量为0.0010-0.0060wt%,硒的作用是吸收光谱中430-540纳米的可见光部分。必要的是要平衡硒和钴的吸收量,以得到中性灰色的外观。
在发明的组合物中,氧化锰的量以MnO2计,为0.10-1.0wt.%。氧化锰可以各种形式添加到配料组份中,如MnO2、MnO4、MnO等。在玻璃组合物中,它通常是以Mn+3和Mn+2的形式存在,但也可以如Mn+4的其它形式存在。在本发明组合物中氧化锰有两种作用:(1)玻璃中的一种形式的锰吸收与硒相同的区域,从而取代一部分硒,(2)氧化锰作为一种氧化剂帮助在配料中保留大部分的硒。通常在没有氧化锰的组合物中,大量昂贵的硒(约85-90%)从配料中挥发了,即使使用了硝酸钠或钾作为氧化剂也是这样。因此我们的这一发现---氧化锰对在最终玻璃产品中保留较高比例的添加到配料中的硒(硒的保留量提高~300%)是特别有利的,对本发明来说是十分重要的。正如上面所讨论和下面将要详细描述的,我们还令人意外地发现与现有技术相反,在玻璃组合物中含有氧化锰和氧化铁不会在暴露于紫外光后引起任何可感觉到的日晒作用(褪色)。我们发现本发明组合物中使用特定量的氧化锰和氧化铁日晒作用会最小。
在本发明的中性灰色玻璃组合物中可以选择性地使用二氧化钛,以促使玻璃组合物达到特殊范围的增强主波长(dominant wavelength)。本发明的灰色玻璃优选激发纯度(excitation purity)小于5.5%的那些。有一点是很重要的,即本发明的玻璃产品应是中性灰色的,特别是绿灰色的;优选使用照明剂C时的主波长为470-590纳米(nm),进一步优选为480-570nm,最优选的是487.5-558nm,使用C.I.E时的观察角度为2°。为使主波长在470-590纳米的范围内变动,二氧化钛是十分有用的。二氧化钛还在光谱曲线的紫外区进行吸收,帮助降低本发明玻璃的紫外透射率。
我们发现,当在4毫米的控制厚度下测量时,本发明的最宽范围的玻璃具有如下光谱性质:使用照明剂A(LTA)时的光透射率为10.0%-55.0%,当玻璃具有小于35.0%的LTA时,紫外透射率小于25.0%,优选小于约10.0%,红外透射率小于约50.0%。很明显,本领域的技术人员根据本发明所公开的内容能用本发明组合物制备其它厚度的玻璃。通常,尽管不是一定要这样限制,但是由平板法生产的玻璃厚度一般在2.0-12.0毫米的范围内。
表2公开了按照本发明优选用来形成中性灰色玻璃组合物的原料的配料组份的量。
表2
配料原料 | 质量范围(kg) |
砂子 | 1000 |
苏打灰 | 290-320 |
白云石 | 215-260 |
石灰石 | 75-90 |
芒硝 | 6-24 |
红铁粉(97%Fe2O3) | 17-23 |
二氧化钛 | 0-5 |
硝酸钠 | 3-20 |
二氧化镁 | 2-8 |
Carbocite(70%C) | 0.1-1.5 |
氧化钴(Co3O4) | 0.30-0.36 |
硒 | 0.20-0.70 |
本领域中的技术人员应当理解,在熔化和加工过程中通常向玻璃配料中添加加工助剂,例如,以维持适当的氧化还原条件的平衡或作为澄清剂。例如,向玻璃组合物中添加Carbocite(无烟煤)具有使一部分Fe2O3还原成FeO以降低红外透射率的效果。在本发明的配料中硝酸钠/或钾是用来在熔化前维持氧化条件,以辅助保留硒。也有使用硝酸盐来改善硒的保留的。必须精心保持Carbocite的还原条件与用来保留硒的硝酸盐和二氧化镁的氧化条件之间的平衡,这是因为氧化剂也作用于氧化铁改变氧化还原平衡,使FeO和Fe2O3之间的氧化还原移动,同时Carbocite改变氧化铁的平衡使之向相反的方向进行。正如上面所描述的,我们发现在本发明组合物中使用特定量的氧化镁和氧化铁能使日晒作用最小。在配料组份中优选使用的芒硝、Carbocite和硝酸钠的量应能在最终组合物中得到两种氧化铁的必要比率,并帮助在本发明的玻璃中减缓日晒作用。更优选地,相对于每1000千克砂子,配料原料的千克数为:芒硝;硝酸钠;Carbocite是8-18;5-15;0.3-1.0,最优选的是8-12;5-10;0.3-1.0。这里所公开的三种配料原料的优选量与最终玻璃产品有关,最终产品的最终组合物中优选具有0.15-0.60wt.%的MnO2和以Fe2O3计的1.2-1.6wt.%的总铁。
本发明中的Carbocite是宾夕法尼亚州Shamokin的Shamokin FillerCompany生产的无烟煤。
为了显示二氧化锰在本发明组合物中改善硒的保留上的令人意想不到的效果,我们制备了8种灰色玻璃组合物,示于下面的表III和表IV。按照本发明方案制备的中性灰色玻璃组合物详细描述在实施例1-4中。为了比较,未用二氧化锰的类似玻璃组合物按实施例5-8所详细描述的方式制备。所有这些玻璃按如下方法制备。配料在实验天平上称重(一般总重为170克),并在玻璃缸中混合10分钟,每一批都使用实验室摇床。每一混合好的配料都放入高为50.8mm(2英寸)、内径为63.5mm(2.5英寸)的铂铑坩埚中,并在每一配料原料中机械地混入4.5ml水。坩埚与其它的3-5个坩埚放入天然气/空气炉中预热到1427℃(2600°F)。在30分钟内炉内温度恢复到1427℃(2600°F)。进行2小时的熔化后,移出每一坩埚,通过在冷水中激冷,使坩埚内的玻璃熔结(fritted),碎片在坩埚内混合,所有坩埚再放回炉中。炉温再提升到1427℃(2600°F),一旦达到了操作温度,按上面描述的步骤重复熔结程序,约45分钟。所有玻璃样品再熔化3小时,并将每一样品注入内径为63.5mm(2.5英寸)的石墨模具中,使之成型以进行下续的砂光(grinding)和抛光。所有样品都放入退火炉,升温到566℃(1050°F),保持4小时,然后使之在16小时内慢慢冷却至室温。对样品进行砂光和抛光,测定每件样品的光谱性质;光谱性质是在控制厚度为4mm下校准的。用X-射线荧光分析法或进行其它必要的测定来分析样品。
表III
实施例1 | 实施例2 | 实施例3 | 实施例4 | |
砂子 | 100.00 | 100.00 | 10.00 | 100.00 |
苏打灰 | 31.41 | 31.41 | 31.41 | 31.41 |
石灰石 | 7.25 | 7.25 | 7.25 | 7.25 |
白云石 | 25.83 | 25.83 | 25.83 | 25.83 |
芒硝 | 1.0956 | 1.0956 | 1.0956 | 1.0956 |
硝酸钠 | 0.5215 | 0.5192 | 0.5233 | 0.5236 |
红铁粉 | 1.8133 | 2.1103 | 1.9683 | 2.1061 |
Carbocite | 0.0916 | 0.0914 | 0.0916 | 0.0907 |
氧化钴 | 0.0142 | 0.0313 | 0.0370 | 0.0392 |
二氧化锰 | 0.5304 | 0.8107 | 1.3750 | 0.5315 |
硒 | 0.0209 | 0.0490 | 0.0430 | 0.0577 |
硒在玻璃中的PPM | 26 | 75 | 70 | 80 |
%保留的硒 | 17.1 | 21.0 | 22.3 | 19.0 |
实施例1-4的本发明的组合物显示,硒的保留量为17.1-22.3%。与此相反,不按本发明(即不含MnO2)的比较实施例5-8显示硒的保留量仅6.8-7.8%。这些实施例表明当按本发明组合物二氧化锰和硒一起使用时硒的保留量几乎提高了300%。
表IV
实施例5 | 实施例6 | 实施例7 | 实施例8 | |
砂子 | 100.00 | 100.00 | 10.00 | 100.00 |
苏打灰 | 31.41 | 31.41 | 31.41 | 31.41 |
石灰石 | 7.25 | 7.25 | 7.25 | 7.25 |
白云石 | 25.83 | 25.83 | 25.83 | 25.83 |
芒硝 | 1.0961 | 1.0960 | 1.0960 | 1.0958 |
硝酸钠 | 0.5187 | 0.5234 | 0.5220 | 0.5188 |
红铁粉 | 2.1078 | 1.8144 | 2.1105 | 2.1051 |
Carbocite | 0.0912 | 0.0913 | 0.0912 | 0.0917 |
氧化钴 | 0.0165 | 0.0144 | 0.0317 | 0.0389 |
硒 | 0.0286 | 0.0414 | 0.0963 | 0.1116 |
硒在玻璃中的PPM | 8 | 10 | 22 | 28 |
%保留的硒 | 7.8 | 6.5 | 6.2 | 6.2 |
下面的表V列出了本发明新的玻璃组合物氧化物组份的优选范围。再下面的表是按本发明优选的玻璃组合物的光谱性质。
表V
优选的玻璃性质范围(玻璃片厚度为4mm)可见光透射率(Ill.A): 16-20%紫外透射率: 5-10%红外透射率: 10-18%总太阳光透射率 12-20%主波长: 470-590nm激发纯度: 0.0-5.5%FeO/总氧化铁(以Fe2O3计)比率 0.18-0.26
氧化物组份 | 重量% |
SiO2 | 71-74 |
Al2O3 | 0.15-0.25 |
Fe2O3 | 1.20-1.60 |
CaO | 8.40-8.70 |
MgO | 3.5-4.00 |
Na2O | 13.00-13.80 |
K2O | 0-0.10 |
TiO2 | 0.00-0.35 |
MnO2 | 0.15-0.6 |
SO3 | 0.14-0.25 |
Co(金属) | 0.0160-0.0185 |
Se(金属) | 0.0020-0.0040 |
按本发明用于制备各种中性灰色玻璃组合物的优选方案的原料量的实施例列于下面的表VI。该表还详细列出了所得玻璃的光谱性质。
表VI
实施例9 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | |
砂子 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
苏打灰 | 31.41 | 31.41 | 31.41 | 31.41 | 31.41 |
石灰石 | 7.25 | 7.25 | 7.25 | 7.25 | 7.25 |
白云石 | 25.83 | 25.83 | 25.83 | 25.83 | 25.83 |
芒硝 | 1.0966 | 1.0959 | 1.0960 | 1.0960 | 1.0961 |
硝酸钠 | 0.5198 | 0.5200 | 0.5205 | 0.5207 | 0.5204 |
红铁粉 | 2.0996 | 2.1008 | 2.1012 | 2.1010 | 2.1142 |
Carbocite | 0.0913 | 0.0910 | 0.0915 | 0.0914 | 0.0913 |
氧化钴 | 0.0300 | 0.0308 | 0.0298 | 0.0305 | 0.0305 |
二氧化锰 | 0.1384 | 0.2705 | 0.2800 | 0.2802 | 0.5601 |
硒 | 0.0550 | 0.0411 | 0.0418 | 0.0415 | 0.0281 |
二氧化钛 | 0.0 | 0.0 | 0.0 | 0.0 | 0.5601 |
%LTA | 18.3 | 18.8 | 17.9 | 19.8 | 19.5 |
%UV | 7.5 | 7.4 | 6.6 | 8.2 | 6.0 |
%IR | 15.7 | 15.6 | 15.2 | 15.0 | 13.1 |
%TSET | 16.7 | 16.8 | 16.1 | 16.9 | 15.5 |
主波长 | 559.8 | 514.3 | 463.7 | 493.9 | 505.5 |
激发纯度,% | 3.3 | 1.3 | 5.1 | 3.8 | 3.2 |
在本发明的整个说明书和上面的表VI中,%LTA定义为用标准照明剂A测定的发光透射率%。%UV是在280-400nm之间测定的紫外透射率,而%IR是在720-2120nm之间测定的红外透射率%。%TSET是按美国专利#4,792,536中的下列方程式测定的总太阳光透射率%:
%TSET=0.44%LTA+0.53%IR+0.03%UV
主波长和%激发纯度是用CIE标准照明剂C测定的。
正如在这里所讨论的,已经知道当暴露于强的紫外光源时,含有氧化锰和氧化铁的玻璃会发生日晒作用或褪色。例如上面讨论过的Jones的专利指出含有氧化铁和MnO2的玻璃是所不希望的,因为在暴露于UV后MnO2会引起棕色。与此相反,本发明的玻璃具有一套在本发明范围内的特殊的氧化还原条件,在上面已经详细地描述了,我们发现它不会经受任何可感觉到的日晒作用。本发明玻璃的实例在加速暴露于Atlas,Model Ci65 Weather-ometer(使用Xenon UV灯)三个月后,其颜色仅有很小的变化。暴露于Atlas,Model Ci65 Weather-ometer三个月被认为在Arizona暴露于太阳光4年。
表VII
开始时 | 暴露3个月后 | 差别 | |
实施例14-实验室融体-无Mn和Ti | 主波长483.0 | 主波长483.2 | +0.2 |
实施例15-实验室融体-0.2%TiO2 | 主波长493.2 | 主波长494.2 | +1.0 |
实施例16-实验室融体-0.2%MnO2 | 主波长568.6 | 主波长570.2 | +1.6 |
实施例17-实验室融体-0.4%MnO2 | 主波长557.0 | 主波长558.4 | +1.4 |
实施例14-实验室融体-无Mn和Ti | %激发纯度5.7 | %激发纯度5.4 | -0.3 |
实施例15-实验室融体-0.2%TiO2 | %激发纯度2.9 | %激发纯度2.6 | -0.3 |
实施例16-实验室融体-0.2%MnO2 | %激发纯度5.1 | %激发纯度5.7 | +0.6 |
实施例17-实验室融体-0.4%MnO2 | %激发纯度3.9 | %激发纯度3.9 | 0.0 |
本发明的范围不仅包括有低透射率的玻璃,还包括能吸热的具有相对高LTA的以及具有中性灰绿色的其它玻璃。这种玻璃的实例详细描述在实施例18和19中,并列于表VIII。
表VIII
实施例18 | 实施例19 | |
砂子 | 100.00 | 100.00 |
苏打粉 | 31.41 | 31.41 |
石灰石 | 7.25 | 7.25 |
白云石 | 25.83 | 25.83 |
芒硝 | 1.0960 | 1.0961 |
硝酸钠 | 0.5204 | 0.5205 |
红铁粉 | 1.3630 | 1.3630 |
Carbocite | 0.0912 | 0.0913 |
氧化钴 | 0.0057 | 0.0095 |
二氧化锰 | 0.2779 | 0.2779 |
硒 | 0.0280 | 0.0210 |
%LTA | 53.2 | 48.7 |
%UV | 23.9 | 23.4 |
%IR | 26.4 | 26.6 |
%TSET | 36.0 | 34.8 |
主波长 | 554.5 | 512.1 |
激发纯度% | 4.3 | 1.8 |
表VIII描述了本发明范围内的玻璃,显示了必须维持钴和硒之间的平衡的灵敏性。增加少量的钴,硒的量减少一点,实施例18的主波长就向实施例19的绿色移动;由于钴和硒的调整,激发纯度也从实施例18向实施例19下降。
Claims (15)
1.一种吸热中性灰色玻璃组合物,按重量计,具有如下基本组成:68-75%的SiO2,10-18%Na2O,5-15%CaO,0-10%MgO,0-5%Al2O3,以及0-5%K2O,其中CaO+MgO为6-15%,Na2O+K2O为10-20%,必要时,有痕量的熔化和澄清助剂,和基本上由0.9-1.9wt.%以Fe2O3计的总的氧化铁;0.002-0.025wt.%的以Co计的钴;0.0010-0.006wt.%以Se计的硒;0.10-1.0wt.%的以MnO2计的氧化锰;以及0.0-1.0wt.%的以TiO2计的氧化钛组成的着色剂;玻璃在4mm的控制厚度下使用照明剂A时的光透射率为10.0%-55.0%,紫外透射率小于25.0%,红外透射率小于50.0%。
2.根据权利要求1的中性灰色玻璃组合物,其特征在于其主波长为470-590纳米。
3.根据权利要求1的中性灰色玻璃组合物,其特征在于在组合物中的SO3的量为0.01-0.03wt.%。
4.一种吸热中性灰色玻璃组合物,按重量计,具有如下基本组成:71-74%的SiO2,13-13.8%Na2O,8.4-8.7%CaO,3.5-4%MgO,0.15-0.25%Al2O3,以及0-0.1%K2O,其中CaO+MgO为6-15%,Na2O+K2O为10-20%,必要时,有痕量的熔化和澄清助剂,和基本上由1.2-1.6wt.%以Fe2O3计的总的氧化铁;0.0160-0.0185wt.%的以Co计的钴;0.0020-0.0040wt.%以Se计的硒;0.15-0.60wt.%的以MnO2计的氧化锰;以及0.0-0.35wt.%的以TiO2计的氧化钛组成的着色剂;玻璃在4mm的控制厚度下使用照明剂A时的光透射率为16.0%-20.0%,紫外透射率为5-10%,红外透射率小于10-18%。其主波长为约470-590纳米。
5.根据权利要求4的中性灰色玻璃组合物,其特征在于其激发纯度为约小于5.5%。
6.根据权利要求3的中性灰色玻璃组合物,其特征在于FeO/以Fe2O3计的总氧化铁为0.18-0.26。
7.根据权利要求1的中性灰色玻璃组合物,其特征在于以制备所述组合物的1000千克砂子配料组份为基础,其它配料组份包括:芒硝6-24千克;硝酸钠3-20千克;Carbocite 0.1-1.5千克。
8.根据权利要求6的中性灰色玻璃组合物,其特征在于所述配料组份包括:芒硝8-18千克;硝酸钠5-15千克;Carbocite 0.3-1.0千克。
9.根据权利要求8的中性灰色玻璃组合物,其特征在于所述配料组份包括:芒硝8-12千克;硝酸钠5-10千克;Carbocite 0.3-1.0千克;所述中性灰色玻璃组合物含有0.15-0.60的MnO2和1.2-1.6wt.%的以计Fe2O3的总铁。
10.一种吸热中性灰色玻璃组合物,按重量计,具有如下基本组成:68-75%的SiO2,10-18%Na2O,5-15%CaO,0-10%MgO,0-5%Al2O3,以及0-5%K2O,其中CaO+MgO为6-15%,Na2O+K2O为10-20%,和基本上由0.9-1.9wt.%以Fe2O3计的总的氧化铁;0.002-0.025wt.%的以Co计的钴;0.0010-0.006wt.%以Se计的硒;0.10-1.0wt.%的以MnO2计的氧化锰;以及0.0-1.0wt.%的以TiO2计的氧化钛组成的着色剂;玻璃在4mm的控制厚度下使用照明剂A时的光透射率为10.0%-55.0%.T,紫外透射率小于25.0%,红外透射率小于50.0%,它是由如下配料原料制成的:砂子、苏打灰、白云石、石灰石、芒硝、红铁粉、硝酸钠、含锰的化合物、Carbocite、含钴的化合物和硒。
11.根据权利要求10的中性灰色玻璃组合物,其特征在于以制备所述组合物的1000千克砂子配料组份为基础,其它配料组份包括:芒硝6-24千克;硝酸钠3-20千克;Carbocite 0.1-1.5千克。
12.根据权利要求11的中性灰色玻璃组合物,其特征在于所述配料组份包括:芒硝8-18千克;硝酸钠5-15千克;Carbocite 0.3-1.0千克。
13.根据权利要求12的中性灰色玻璃组合物,其特征在于所述配料组份包括:芒硝8-12千克;硝酸钠5-10千克;Carbocite 0.3-1.0千克;所述中性灰色玻璃组合物含有0.15-0.60的MnO2和1.2-1.6wt.%的以计Fe2O3的总铁。
14.一种由权利要求1的中性灰色玻璃组合物制备的用于汽车或建筑上的玻璃的砑光(glazing)。
15.一种制备中性灰色玻璃组合物的方法,该组合物在4mm的控制厚度下使用照明剂A时的光透射率为10.0%-55.0%,紫外透射率小于25.0%,红外透射率小于50.0%,基本上包括将砂子、苏打灰、白云石、石灰石、芒硝、红铁粉、硝酸钠、含锰化合物、Carbocite、含钴化合物和硒混合并一起熔化,其量应足以形成权利要求1的玻璃。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/168,347 US5346867A (en) | 1993-12-17 | 1993-12-17 | Neutral gray absorbing glass comprising manganese oxide for selenium retention during processing |
US08/168,347 | 1993-12-17 |
Publications (2)
Publication Number | Publication Date |
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CN1137785A CN1137785A (zh) | 1996-12-11 |
CN1039404C true CN1039404C (zh) | 1998-08-05 |
Family
ID=22611154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN94194503A Expired - Fee Related CN1039404C (zh) | 1993-12-17 | 1994-11-14 | 含有能在加工过程中保持硒的氧化锰的中性灰色吸收玻璃 |
Country Status (9)
Country | Link |
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US (2) | US5346867A (zh) |
EP (1) | EP0734358B1 (zh) |
JP (1) | JP2892839B2 (zh) |
KR (1) | KR100308331B1 (zh) |
CN (1) | CN1039404C (zh) |
CA (1) | CA2179146A1 (zh) |
DE (1) | DE69405011T2 (zh) |
ES (1) | ES2105870T3 (zh) |
WO (1) | WO1995016641A1 (zh) |
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- 1994-11-14 KR KR1019960702750A patent/KR100308331B1/ko not_active IP Right Cessation
- 1994-11-14 CN CN94194503A patent/CN1039404C/zh not_active Expired - Fee Related
- 1994-11-14 ES ES95900839T patent/ES2105870T3/es not_active Expired - Lifetime
- 1994-11-14 JP JP7516581A patent/JP2892839B2/ja not_active Expired - Lifetime
- 1994-11-14 CA CA002179146A patent/CA2179146A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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CN1137785A (zh) | 1996-12-11 |
US5521128A (en) | 1996-05-28 |
DE69405011T2 (de) | 1998-01-08 |
WO1995016641A1 (en) | 1995-06-22 |
JPH09506584A (ja) | 1997-06-30 |
DE69405011D1 (de) | 1997-09-18 |
CA2179146A1 (en) | 1995-06-22 |
ES2105870T3 (es) | 1997-10-16 |
US5346867A (en) | 1994-09-13 |
KR100308331B1 (ko) | 2001-11-30 |
KR960705749A (ko) | 1996-11-08 |
EP0734358B1 (en) | 1997-08-13 |
EP0734358A1 (en) | 1996-10-02 |
JP2892839B2 (ja) | 1999-05-17 |
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