CN107428596A - 玻璃 - Google Patents

玻璃 Download PDF

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CN107428596A
CN107428596A CN201680018348.0A CN201680018348A CN107428596A CN 107428596 A CN107428596 A CN 107428596A CN 201680018348 A CN201680018348 A CN 201680018348A CN 107428596 A CN107428596 A CN 107428596A
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M·J·霍斯利
S·泰勒
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Pilkington Group Ltd
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Abstract

公开了玻璃,其具有包含以下氧化物的组成(重量%):SiO2 61‑70%,Al2O3 0‑9%,Na2O 10‑13%,K2O 0‑1%,MgO 2‑6%,CaO 6‑16%,SrO 1‑8%,ZrO2 0‑10%,TiO2 0‑10%。玻璃可能具有大于570℃的应变点,并且在高温下具有良好的尺寸稳定性,使得它们适用于在升高的温度下加工的防火玻璃和基材,例如用于显示面板,信息存储盘和半导体器件包括光伏电池的基材。公开了玻璃的物理性质,例如热膨胀系数,密度和折射指数,以及熔化和液相线温度。该玻璃适用于通过浮法工艺制造,以片材形式生产平板玻璃。

Description

玻璃
本发明涉及玻璃,更具体地涉及新玻璃、新玻璃组合物和由新玻璃组合物构成的基材。新玻璃组合物是钠钙硅玻璃,但与已知的钠钙硅玻璃,特别是通常用于通过浮法工艺生产平板玻璃的那些钠钙硅玻璃相比具有相对高的应变点。因此,本发明的新玻璃适用于在高温下需要良好尺寸稳定性的应用,例如防火窗玻璃和用于在高温下加工的基材。这些基材适用于涂层的沉积和显示面板、盘例如磁记录盘、半导体器件包括光伏电池,特别是太阳能电池的制造等应用。
虽然普通钠钙硅玻璃(即常用于建筑物和车辆的窗户和其他窗玻璃的钠钙硅玻璃组合物)对于许多上述应用具有在室温下的合适性能,但是这些应用可能需要在高温下加工玻璃,即在高于应变点,或退火点,或甚至玻璃的软化点的温度下。在这样升高的温度下加工玻璃会导致在玻璃中产生永久的内部应力,可能导致玻璃的变形或断裂。在加工过程中,玻璃甚至可变得畸变或变形。因此,已经尝试提供更适合于高温加工的玻璃,即由于具有相对高的应变点而具有改善的高温稳定性的玻璃。
通常使用的钠钙浮法玻璃的应变点(其定义为玻璃的粘度为1014.5泊的温度,表示为T log 14.5泊)在约510℃至540℃的范围内,取决于精确的组成。然而,许多具有较高应变点的玻璃是已知的。具有高应变点的一组玻璃是所谓的无碱玻璃。遗憾的是,这些玻璃由于缺乏作为助熔剂的碱而难以生产。这些玻璃中的许多也不适合通过浮法工艺成型。替代的成型方法的使用通常增加成本,并且可导致较差的表面平坦度或平滑度。无碱玻璃的另一个问题是它们倾向于具有非常低的热膨胀系数,这使得它们不适于某些应用。
与普通或“正常”的钠钙硅浮法玻璃相比,具有相对高应变点的另一组玻璃含有增加的钾碱和降低的苏打。遗憾的是,高钾碱玻璃本身难以在浮法车间中常用的开放式蓄热炉中生产,因为在这种炉中可能难以澄清高钾碱玻璃。
已经进行了许多尝试以提供比具有普通浮法玻璃更高的应变点的钠钙硅玻璃组合物。US 5,599,754公开了一种用于基材的玻璃组合物,其可用于平板显示面板,特别是用于等离子体显示面板。所要求保护的组合物含有6至9%的SrO。
US 6,905,991是含有相对低水平的苏打(2-8%Na2O)和相对高水平的钾碱(0-8%,但是所有实施例包含至少3.5%的K2O)的钠钙硅玻璃组合物的实例。所得玻璃可用于生产防火窗玻璃板或用于显示面板的基材。
WO 98/49111公开了一种用于等离子体显示面板的玻璃组合物,该玻璃具有比以前用于等离子体显示面板的玻璃更低的密度。玻璃中的总碱土金属氧化物中所含的BaO和SrO的总量在1-8%的范围内。
US 6,087,284涉及适用于显示技术的铝硅酸盐玻璃。该专利试图找到具有高转变温度、低密度且中途曝光(solarisation)稳定的玻璃。优选玻璃含有最多痕量的MgO或完全不含。因此它代表了与普通或通常浮法玻璃的组成的显著偏差。
US 7,273,668涉及一种适用于化学强化的具有高耐热性的玻璃组合物。该组合物可用于制备用于磁记录介质的玻璃基材,例如硬盘驱动器。遗憾的是,这种玻璃容易失透,这可能使制造困难,并降低产量。
KR 2009 0111680A公开了用于显示面板的玻璃组合物,其寻求改善电极图案的反应性和故障率。
JP 2010 143790A公开了一种太阳能电池的玻璃基材的制造方法,其中可以有效地回收废玻璃。废玻璃用作玻璃原料的一部分,然后将其在玻璃熔炉中熔化并成型为玻璃基材。
US 8,828,897涉及具有高热稳定性和低加工温度的铝硅酸盐玻璃。该玻璃可用作光伏应用和其它太阳能技术应用的基材玻璃,顶衬玻璃和/或覆盖玻璃。
US 8,895,463涉及一种用于太阳能电池例如Cu-In-Ga-Se(“CIGS”)太阳能电池的玻璃基材。该发明的玻璃组成显著偏离普通钠钙硅玻璃,低苏打和高钾碱。
US 2013/0306145 A1还涉及用于CIGS太阳能电池的玻璃基材,并且玻璃组成仍是低苏打和高钾碱。
US 2013/0313671 A1涉及用于太阳能电池例如CdTe或CIGS电池的玻璃基材。据说,SrO、BaO、B2O3和/或ZrO2的含量有利地为零,以便不损害玻璃片材的成本。然而,经判断所提供的实施例,与普通钠钙硅玻璃相比,该方法仅产生应变点的适中增加。
期望提供实现应变点的显著增加的新玻璃,而无玻璃成本的显著增加。玻璃的成本包括原材料的成本以及将其转变为成品玻璃片材的成本,其本身包括燃料、劳动力、所用工厂的成本、其效率水平、所获得的产量等因素。因此,进一步希望提供新的玻璃组合物,其实现应变点的显著增加,并且还能够通过浮法工艺容易地制造,因为该工艺是制造平板玻璃的非常有效的方式。因此,所期望的新玻璃组合物是适于经济制造的组合物。
已经令人惊奇地发现,将SrO添加到普通浮法玻璃组合物中产生玻璃应变点的显著增加。
根据本发明,提供一种具有包含下述氧化物(重量%)的组成的玻璃:
还发现,除了SrO之外,向玻璃组合物中添加Al2O3、ZrO2或TiO2也进一步增加了玻璃的应变点。
根据本发明的玻璃适合在比普通浮法玻璃更高的温度下加工。本发明的玻璃在升高的温度下不易变形或畸变,因此具有较高的尺寸稳定性和改善的耐热性。
优选地,玻璃组合物包含以下范围内的特定氧化物(重量%):
有利地,玻璃组合物包含3-7%的SrO,优选3-6%的SrO,更优选4-6%的SrO。任选地,这种玻璃组合物还可含有3-9%的Al2O3,优选4-8%的Al2O3。玻璃组合物还可以含有2-7%的ZrO2,优选3-7%的ZrO2。玻璃组合物还可以含有2-7%的TiO2,优选3-6%的TiO2。由于氧化锶(SrO)比用于制造浮法玻璃的其它原材料贵,这允许定制根据本发明的玻璃以实现性能和成本之间的期望的平衡。
任选地,玻璃组合物不含任何一种或任何数量的以下氧化物:As2O3、BaO、B2O3、BeO、CeO2、Er2O3、GeO2、Li2O、P2O5、PbO、Sb2O3、SnO2、TiO2、V2O5、ZnO、ZrO2。由于毒性、成本或其对炉结构的不利影响的原因,这些氧化物可能是令人不快的。然而,由于原料中的杂质,可能存在痕量的这些氧化物。特别地,玻璃组合物可含有0至1%的BaO或B2O3。或者,玻璃可以基本上不含B2O3,因为本发明的玻璃通常不是硼硅酸盐。在考虑的许多应用中,不需要或不希望使玻璃着色,因此在这种情况下,玻璃不含着色剂,例如CdO、CeO2、CoO、Co3O4、Cr2O3、CuO、Er2O3、MnO2、Nd2O3、NiO、Se、V2O5。总铁含量可以在0.01-1%之间,优选在0.01-0.5%之间,最优选在0.01-0.3%之间(以Fe2O3表示)。然而,当玻璃用作基材时,铁含量通常是次要的,因为基材的光透射通常是不重要的。这同样适用于基材的紫外、可见和红外透射。
优选地,根据本发明的玻璃具有大于570℃,优选大于580℃,更优选大于585℃,更优选大于590℃的应变点。如上所述,期望提供容易通过浮法工艺制造的玻璃。因此,在增加玻璃的应变点的同时,考虑玻璃的其它性质,如熔化温度、液相线温度和热加工温度范围也是重要的,这决定了玻璃如何易于熔化和成型。令人惊奇的是,本发明人能够同时调整所有这些性能以提供具有高应变点和良好制造性能的玻璃。
优选地,根据本发明的玻璃具有小于1500℃,优选小于1480℃,更优选小于1460℃的熔化温度(定义为粘度为100泊的温度,即log 2泊,表示为T log 2泊)。这允许原料熔化并变成玻璃而无过多的燃料使用,并且不会对熔化玻璃的炉的结构造成不当的磨损。
有利地,根据本发明的玻璃的液相线温度低于1200℃,优选小于1180℃,更优选小于1160℃,更优选小于1140℃,更优选小于1120℃,最优选小于1100℃。较低的液相线温度降低了在炉的较冷区域中的熔化玻璃的失透风险。术语“失透”是指在玻璃中形成晶体诸如硅灰石(在下表I中称为“Woll.”)或透辉石,这是不期望的,因为这样的晶体可出现在最终产物,使其不合格。
期望地,根据本发明的玻璃具有大于-100℃,优选大于-80℃,更优选大于-60℃,更优选大于-40℃,更优选大于-20℃,最优选大于0℃的热加工温度范围(定义为成型温度,T log 4泊,减去液相线温度),最优选热加工温度范围为正数。一些玻璃成型工艺比其他玻璃成型工艺更容忍负数热加工温度范围,且浮法玻璃工艺能够在负数热加工温度范围内操作。较不负数或较正数的热加工温度范围有助于熔化玻璃成型为产品(例如平板玻璃带),而不发生失透。
对于最终产品(例如玻璃片材、玻璃基材、显示面板、盘等)的物理性质来说,适合于玻璃的特定目标应用是有利的。对于这些应用中的一些,普通钠钙硅玻璃在室温下具有合适的物理性能,但如前所述,它不能在足够高的温度下加工而没有负面影响。根据本发明的另一方面,提供了不仅具有增加的应变点并适合于经济制造,而且在室温下保持适当物理性质的玻璃。
例如,根据本发明的这个方面,提供一种玻璃,其具有70-90×10-7-1(50-350℃),优选72-88×10-7-1(50-350℃),更优选74-86×10-7-1(50-350℃),最优选76-84×10-7-1(50-350℃)的热膨胀系数。
此外,当由炉产生的玻璃从一种组成转变成另一种组成时,诸如密度和折射指数的性质也是重要的。特别重要的转化是从普通浮法玻璃向根据本发明的玻璃转化。这样的转化是在“运行中(on the run)”进行的,即将进料到炉中的原料混合物转化成适合于该新组成的混合物,而不排空炉子或停止熔化。如果两种玻璃组成具有相似的密度和折射指数,则可以减少转化所花费的时间,因为这时两种组成的混合更容易发生。
因此,也希望提供具有在25℃下2.50-2.70g cm-3,优选在25℃下2.51-2.69g cm-3,更优选在25℃下2.52-2.68g cm-3,进一步优选在25℃下2.53-2.67g cm-3,更加优选在25℃下2.54-2.66g cm-3,最优选在25℃下2.55-2.66g cm-3的密度的玻璃组合物
类似地,如果根据本发明的玻璃具有1.50-1.62,优选1.51-1.60,更优选1.52-1.59,更优选1.53-1.58的折射指数,则这是期望的。
本发明还包括具有根据所附权利要求的玻璃组成的玻璃制品,特别是由具有本文所要求保护的玻璃组成的玻璃形成的玻璃片材。此外,本发明还包括玻璃基材,其包含具有本文所要求保护的玻璃组成的玻璃和使用这种玻璃基材制造的任何产品,包括但不限于显示面板、盘、半导体器件和光伏电池,特别是太阳能电池。根据本发明的玻璃基材可以用于CdTe和CIGS(Cu-In-Ga-Se)太阳能电池等。
现在将参考表1中列出的以下非限制性实施例进一步描述本发明。在该表中,实施例11和20是根据本发明的,其余的实施例即实施例1至10和12至19是比较例。特别地,实施例1是普通浮法玻璃的代表且具有536℃的应变点。相比之下,实施例2-20具有574℃-595℃的应变点,根据本发明的实施例分别具有579℃和574℃的应变。
虽然一些比较例具有较高的应变点,但其中一些也具有较大的负数热加工温度范围。例如,虽然实施例7具有595℃的应变点,但该实施例也具有-199℃的热加工温度范围。相反,实施例11和20分别具有+57℃和-69℃的热加工温度范围。在实施例11的情况下,这部分是由于1030℃的非常低的液相线温度,这意味着在制造该玻璃时不太可能遇到失透问题。
因此,具有根据本发明的玻璃组成的新玻璃提供显著增加的应变点,同时保持适当的制造和室温性质,使其适合于高温加工和在升高温下需要增加的尺寸稳定性的其它应用。
表1
表1(续)
表1(续)

Claims (13)

1.玻璃,具有包含以下氧化物的组成(以重量%计):
2.根据权利要求1所述的玻璃,其包含以下氧化物(以重量%计):
3.根据权利要求1或2所述的玻璃,其包含3-7%的SrO,优选3-6%的SrO,更优选为4-6%的SrO。
4.根据前述权利要求中任一项所述的玻璃,其具有大于570℃,优选大于580℃,更优选大于590℃的应变点。
5.根据前述权利要求中任一项所述的玻璃,其具有小于1500℃,优选小于1480℃,更优选小于1460℃的熔化温度(在该温度下粘度=log 2泊)。
6.根据前述权利要求中任一项所述的玻璃,其具有小于1200℃,优选小于1180℃,更优选小于1160℃,更优选小于1140℃,更优选小于1120℃,最优选小于1100℃的液相线温度。
7.根据前述权利要求中任一项所述的玻璃,其具有大于-100℃,优选大于-80℃,更优选大于-60℃,更优选大于-40℃,更优选大于-20℃,最优选大于0℃的热加工温度范围(定义为液相线温度减去Tlog 4泊)。
8.根据前述权利要求中任一项所述的玻璃,其具有70-90×10-7_1(50-350℃),优选74-86×10-7_1(50-350℃)的热膨胀系数。
9.根据前述权利要求中任一项所述的玻璃,其具有在25℃下2.50-2.70g cm-3,优选在25℃下2.52-2.68g cm-3,更优选在25℃下2.54-2.66g cm-3的密度。
10.根据前述权利要求中任一项所述的玻璃,其具有1.50-1.62,优选1.52-1.59,更优选1.53-1.58的折射指数。
11.玻璃片材,由根据前述权利要求中任一项所述的玻璃形成。
12.玻璃基材,包含根据前述权利要求中任一项所述的玻璃。
13.光伏电池,包含根据权利要求12所述的玻璃基材。
CN201680018348.0A 2015-03-26 2016-03-23 玻璃 Pending CN107428596A (zh)

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