CN1043751C - 供制作玻璃板的玻璃组合物 - Google Patents

供制作玻璃板的玻璃组合物 Download PDF

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CN1043751C
CN1043751C CN94113876A CN94113876A CN1043751C CN 1043751 C CN1043751 C CN 1043751C CN 94113876 A CN94113876 A CN 94113876A CN 94113876 A CN94113876 A CN 94113876A CN 1043751 C CN1043751 C CN 1043751C
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glass
feo
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CN1109848A (zh
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P·让沃伊内
M·里斯蒙迪
J·韦斯莱特
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Saint Gobain Vitrage SA
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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
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • 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
    • C03C4/08—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
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y10T428/31612—As silicone, silane or siloxane
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31627—Next to aldehyde or ketone condensation product
    • Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31645—Next to addition polymer from unsaturated monomers

Abstract

本发明涉及适宜于制作尤其能用于建筑方面或可在机动车和工业运输车上的玻璃板的玻璃组合物。
本发明的玻璃组合物以重量百分数表示含有0.75-1.4%以Fe2O3形式表示的总铁，0.25-0.32%以FeO形式表示的亚铁，其厚度为约3-3.3毫米时在发光体A(TLA)下的总光透射系数至少为70%，总能量透过系数(TE)低于约46%，紫外辐射透射系数低于约25%。

Description

供制作玻璃板的玻璃组合物
本发明涉及适宜于制作玻璃板，尤其是能够用于建筑方面或机动车与工业运输车上按装的玻璃板的玻璃组合物。
后一类使用的玻璃板应当满足有关透光性法定要求。因此，供制作风挡的玻璃板的总光透射系数在发光体A(TLA)下至少为75％。供制作侧面和后窗的玻璃板，在同样的条件下其系数TLA至少为70％。
机动车装玻璃的面积实际上是很重要的，买主对舒适方面的要求变得越来越高，这些车辆的设计师们研究过能够减弱受太阳光照射的乘客的所感受到热量的任何办法。
为了保持可见光谱部分的高透光性，同时尽可能吸收余下的太阳能，人们都知道在玻璃组合物中加入铁。铁在玻璃中同时以铁氧化物(Fe2O3)和亚铁氧化物(FeO)两种形式存在。
Fe2O3能吸收紫外辐射，并且该辐射在可见光谱部分是短波长的；相反地，FeO能吸收近红外辐射，该辐射相应于可见光区域长波长。
如果铁的两种氧化形式含量增加，提高了可见光谱两端的辐射吸收，这种作用导致透光性变差。
目前，为了最好地利用吸收辐射的铁氧化物而又保持可能的最大透光性，曾提出几种不同的解决方案。
因此，EP-B-297404描述并要求保护硅-钠-钙玻璃，其总铁含量(以Fe2O3形式表示)为0.45-0.65％。这些玻璃应在总铁中至少35％，最好50％为FeO形式的条件下制造。这样增加FeO含量能提高玻璃的红外吸收，并且能降低总能量透过系数(TE)。然而，当在强还原条件下在硫存在的情况下制造玻璃时，由于硫与三价铁反应生成发色团而带来琥珀色。为了避免这一点，那么必须除去可玻璃化混合物中的硫酸盐，并且由于玻璃中硫含量从未为零，还必须保证三价铁的百分数是很低的，这样导致大大限制了总铁含量。于是，这些玻璃吸收紫外线辐射的能力就很一般。
人们还知道，由于总铁含量比上述欧洲专利所提出的含量更高，制出的玻璃具有良好透光性和良好的红外和紫外辐射吸收。
US-A-5214008描述了无四价铯氧化物和这类其他氧化物的玻璃，该玻璃含0.7-0.95％(重量)以Fe2O3形式表达的总铁。这种玻璃是用一般的能玻璃化原料在普通炉子中制成的。由于在能玻璃化的混合物中加入碳和硫酸钠，所以控制了玻璃的氧化还原度。
这种氧化还原度在正确的范围内变动，如玻璃中FeO形式的铁在0.19-0.24％(重量)范围内变动，所述玻璃的厚度为3.7-4.8毫米时，其光透射系数超过70％，紫外区透射系数小于38％，总能量透过系数小于44.5％。
硅-钠-钙玻璃的其他组合物，在一定的厚度条件下可得到光透射系数至少为70％，并具有良好的红外和紫外辐射吸收。在EP-A-488110和WO-91/07356申请中描述组合物尤其是这种情况。除铁的氧化物外，这些专利申请所描述的玻璃都含有铈氧化物和钛氧化物。如果这些氧化物能提高紫外辐射线吸收，则它们的应用并非优越。
同样，铈氧化物是一种相当昂贵的组分，使用它就构成了玻璃的主要成本，该氧化物还对不利于亚铁氧化物的亚铁氧化物与三价铁氧化物的平衡产生影响。作为其部分的钛氧化物的缺陷是降低可见光区的透光性。
本发明的目的在于一种玻璃，在熔融金属浴表面上它能成层，其透射特性主要通过铁的氧化物进行调节，并且与已知的可比较的玻璃相比，其吸收红外与紫外辐射的能力与所述玻璃的能力至少是等级的，但厚度比较小。
通过硅-钠-钙玻璃组合物，其中含有(以重量百分数表示)0.75-1.4％以Fe2O3形式表示的总铁，0.25-0.32％以FeO形式表示的亚铁，可以达到本发明目的，所述玻璃组合物的厚度为约3-3.3毫米时，在发光体A(TLA)下总光透射系数至少为70％，总能量透过系数(TE)低于约46％，紫外辐射透射系数小于约25％。光和能量透射值是根据Parry Moon Mass2方法测定的。紫外区域透射值是根据ISO9050标准定义的方法测定的。
本发明的玻璃是用目前使用的原料在浮法玻璃技术中使用的普通炉子中制造的。本发明玻璃的熔化与精炼是在火焰喷射炉(desfours a flammes)中进行的，其炉可能装有电极，而电极可以保证电流在所述电极之间通过时加热块状玻璃。本发明玻璃的氧化还原度可藉助诸如硫酸钠之类的氧化剂和诸如焦炭之类的还原剂进行控制。在能玻璃化的混合物中加入硫酸钠的量，应考虑熔化该混合物的炉子特性，其量是如玻璃的SO3含量一般是0.10-0.35％。
还应考虑制造玻璃的炉子特性，计算出与硫酸盐相关的还原剂含量，以便可以将所述玻璃的氧化还原度保持在正确的范围内。这些范围是用以FeO形式表示的亚铁量与以Fe2O3形式表示的总铁量之比的极值限定的。按照本发明，FeO/Fe2O3之比为22-34％；优选为25-30％。
本发明的玻璃是硅-钠-钙玻璃，它有以下成分，其含量是由下面用重量百分数的范围限定的：
    SiO2     64-75％
    Al2O3     0-5％
    B2O3     0-5％
    CaO     2-15％
    MgO     0-5％
    Na2O     9-18％
    K2O     0-5％
    Fe2O3(以这种形式表示的总铁)     0,75-1,4％
    FeO     0,25-0,32％
    SO3     0,10-0,35％
本发明的玻璃还可能含有看作杂质的由所使用的能玻璃化的原料和/或由能玻璃化混合物中加入的玻璃屑带来的其他组分，还含有如铁氧化物之类的其他少量着色剂。这些杂质为玻璃重量的0.1％以下；例如钛、钴、镍、铬、硒或锰便是如此。
本发明的玻璃最好含0.85-1.3％以Fe2O3表示的总铁。
在本发明的玻璃中，总铁含量与亚铁氧化物和三价铁氧化物各个含量的控制便能以相当小的厚度得到红外与紫外辐射的显著吸收。当这种玻璃用于制作薄玻璃板时，这是特别有利的。
除了前述的透射特性外，本发明的玻璃具有一种近似于兰-绿色的色彩。在发光体C下它们的特征波长一般为490-505纳米。
下面作为实施例给出的玻璃将能看到本发明玻璃的优点。
为得到100克这种玻璃所使用的能玻璃化混合物如下：
砂                    63克
石灰                  5.7克
白云石                21.4克
霞石                  0.90克
碳酸钠                27.3克
硫酸钠                0.75克
铁丹                  0.9克
焦炭                  0.035克以重量百分数表示的所得到的玻璃分析结果如下：
SiO2           70,57％
Al2O3          0.62％
CaO              6,50％
MgO              3,90％
Na2O            13,90％
K2O             0,09％
SO3             0,18％
Fe2O3(总铁)    0,95％
FeO              0,285％
FeO/总铁         0,30％
正如前面明确指出，所测量的这种玻璃厚度为3.15毫米时的透射特性如下：
TLA        71％
TE         43,5％
TUV        18％
这种玻璃在发光体C下的特征波长为499纳米。
采用浮法玻璃技术时可将本发明玻璃转变成连续带状玻璃。切割该带是玻璃得到玻璃薄板，其厚度为1-5毫米。这些玻璃薄板可以单独或配合使用以便用来制作尤其可按装在机动车上的玻璃板。
为了制作风挡或侧面玻璃，人们使用单独一块玻璃或由有机物夹层分隔的二块玻璃。玻璃总厚度往往为3-4毫米。本发明的玻璃为这些厚度时可保证良好的紫外线吸收和良好的热舒适性。
如同其他玻璃板，由本发明的玻璃得到的玻璃板可预先进行表面处理，或可以与有机涂层(如具有抗刮擦性能的聚氨酯为主要成分的薄膜或保证在破裂情况下密封性的薄膜)组合起来；可以在局部复盖诸如一层釉层。
本发明的玻璃板可以复盖至少一层金属氧化物，金属氧化物是采用热解技术在高温下化学沉积，或蒸汽相化学沉积(CVD)或其它沉积得到的。

Claims (4)

1．玻璃板，其中包括至少一块玻璃薄板，其化学组成中含有下列组分，而按重量百分比计各组分在玻璃中的含量如下：
SiO2                            64-75％
Al2O3                          0-5％
B2O3                           0-5％
CaO                              2-15％
MgO                              0-5％
Na2O                            9-18％
K2O                             0-5％
Fe2O3(以该形式表示的总铁含量)  0.85-1.4％
FeO                              0.25-0.32％
SO3                             0.10-0.35％
以及可能情况下的杂质             少于0.1％
厚度为3-3.3mm的所述玻璃在发光体A(TLA)下的总光透射
系数至少70％，总能量透过系数(TE)小于46％，紫外辐射透射系数小于约25％。
2．按照权利要求1所述的玻璃板，其特征在于以FeO表示的亚铁含量为以Fe2O3表示的总铁含量的22-34％。
3．按照权利要求2所述的玻璃板，其特征在于以FeO表示的亚铁含量为以Fe2O3表示的总铁含量的25-30％。
4．按照上述权利要求中任何一项所述的玻璃板，其特征在于玻璃中以Fe2O3表示的总铁含量为0.85-1.3％。
CN94113876A 1993-09-17 1994-09-16 供制作玻璃板的玻璃组合物 Expired - Lifetime CN1043751C (zh)

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FR9311129 1993-09-17
FR9311129A FR2710050B1 (fr) 1993-09-17 1993-09-17 Composition de verre destinée à la fabrication de vitrages.

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CN1109848A CN1109848A (zh) 1995-10-11
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CA (1) CA2132147C (zh)
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CZ (1) CZ286292B6 (zh)
DE (1) DE69419989T2 (zh)
ES (1) ES2135550T3 (zh)
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KR950008398A (ko) 1995-04-17
US5700579A (en) 1997-12-23
PL178552B1 (pl) 2000-05-31
FR2710050A1 (fr) 1995-03-24
JPH07330371A (ja) 1995-12-19
DE69419989D1 (de) 1999-09-16
ES2135550T3 (es) 1999-11-01
CZ228294A3 (en) 1995-10-18
PL305070A1 (en) 1995-03-20
US5817587A (en) 1998-10-06
RU94033485A (ru) 1996-07-20
CA2132147C (fr) 2004-05-18
BR9403753A (pt) 1995-05-16
EP0644164B1 (fr) 1999-08-11
EP0644164A1 (fr) 1995-03-22
FR2710050B1 (fr) 1995-11-10
CN1109848A (zh) 1995-10-11
CA2132147A1 (fr) 1995-03-18
JP4213227B2 (ja) 2009-01-21
CZ286292B6 (cs) 2000-03-15
CO4370055A1 (es) 1996-10-07
DE69419989T2 (de) 2000-01-27
KR100358821B1 (ko) 2003-01-08

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