CN102171154A - 中等热膨胀系数的玻璃 - Google Patents
中等热膨胀系数的玻璃 Download PDFInfo
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- CN102171154A CN102171154A CN2009801404052A CN200980140405A CN102171154A CN 102171154 A CN102171154 A CN 102171154A CN 2009801404052 A CN2009801404052 A CN 2009801404052A CN 200980140405 A CN200980140405 A CN 200980140405A CN 102171154 A CN102171154 A CN 102171154A
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- 239000011521 glass Substances 0.000 title claims description 198
- 239000000463 material Substances 0.000 claims description 23
- 229910052728 basic metal Inorganic materials 0.000 claims description 21
- 150000003818 basic metals Chemical class 0.000 claims description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000004927 fusion Effects 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
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- 230000002860 competitive effect Effects 0.000 description 2
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- 238000004031 devitrification Methods 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000006105 batch ingredient Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 239000005400 gorilla glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
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- C03C3/00—Glass compositions
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- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C03C3/00—Glass compositions
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- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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Abstract
本发明描述了可以用于光伏用途、光致变色用途、电致变色用途或有机发光二极管(OLED)照明用途的铝硼硅酸盐玻璃。
Description
本申请要求2009年10月5日提交的美国专利申请第12/573213号的优先权,后者要求2008年10月6日提交的美国临时申请第61/103126号的优先权,还要求2009年5月13日提交的美国临时申请第61/177827号的优先权。
背景技术
技术领域
实施方式一般涉及铝硼硅酸盐玻璃,更具体涉及低碱铝硼硅酸盐玻璃,所述玻璃可以用于光伏用途、光致变色用途、电致变色用途或者有机发光二极管(OLED)照明用途。
背景技术
熔合成形法通常可以制得具有适合用于许多电子用途的最优表面和几何特征的平板玻璃,例如电子应用中的基板,例如LCD电视机的显示器玻璃。
在过去的10年中,康宁公司(Corning)的熔合玻璃产品包括1737FTM,1737GTM,Eagle2000FTM,EagleXGTM,JadeTM以及Codes 1317和2317(Gorilla GlassTM)。通常认为在使得熔体粘度约为200泊(p)的特定温度下发生了高效的熔融。这些玻璃的200p温度都超过了1600℃,这会加快容器和电极的腐蚀,因为澄清器的温度更高,所以对澄清的要求更高,并且/或者导致铂体系的寿命缩短,特别是在澄清器周围。许多玻璃粘度达到3000泊的温度约高于1300℃,因为这是光学搅拌器常规的粘度,该粘度下的高温会导致过度的搅拌器磨损以及玻璃主体内增加的铂缺陷水平。
许多上述玻璃的传输温度超过1200℃,这会促进等压槽(isopipe)耐火材料的蠕变,对于大片材尺寸的情况尤其明显。
这些特性结合起来,限制流动(因为熔体速率缓慢),加快了设备的劣化,迫使以远小于产品寿命的时间表进行重建,迫使人们为了消除缺陷而采取无法接受的(使用砷的方法),昂贵的(包封)或不实用的(真空澄清化)方案,由此显著地提高了制造玻璃的成本。
在需要对性能要求不太极端的较为廉价的较厚的玻璃的应用中,不仅对这些玻璃有些矫枉过正,而且由于过于昂贵而无法制造。当通过浮法制造竞争材料的时候,这一问题特别明显,所述浮法是一种非常好的方法,可以制得具有常规性质的低成本的玻璃。在对成本敏感的应用,例如大面积光伏面板和OLED照明中,这种成本差异过大,使得LCD型玻璃的价格无法接受。
为了降低该成本,优选降低最大的整体成本因子(除了澄清化以外),许多方法涉及熔融和成形工艺采用的温度。因此,人们需要熔融温度低于上述玻璃的玻璃。
另外,优选需要能够用于低温用途的玻璃,例如用于光伏用途和OLED照明用途。另外,优选使得玻璃的加工温度足够低,使得制造玻璃的时候无需过度消耗能量,这些用途可以节约能量。
发明内容
一个实施方式是一种玻璃,其包含:
60-65摩尔%的SiO2;
8-12摩尔%的Al2O3;
7-15摩尔%的B2O3;
大于0摩尔%至8摩尔%的M2O;
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
这种玻璃解决了常规玻璃的一个或多个上述缺陷,并提供一个或多个以下优点:加入玻璃的碱金属可以显著加快熔融,允许获得更高的牵拉速率和较低的熔融温度。它们还可以增大热膨胀系数,因此可以更好地与例如CdTe光伏装置匹配。
在以下的详细描述中提出了本发明的附加特征和优点,其中的部分特征和优点对本领域的技术人员而言由所述内容而容易理解,或按文字描述和其权利要求书以及附图中所述实施本发明而被认识。
应理解前面的一般性描述和以下的详细描述都只是对本发明的示例,用来提供理解要求保护的本发明的性质和特性的总体评述或框架。
包括的附图提供了对本发明的进一步理解,附图被结合在本说明书中并构成说明书的一部分。附图图示说明了本发明的一个或多个实施方式,并与说明书一起用来说明本发明的原理和操作。
附图简要说明
仅通过以下详述或与附图一起可更好地理解本发明。
图1是预测的液相线粘度图。
图2是根据一个实施方式的光伏装置的特征的示意图。
具体实施方式
下面详细说明本发明的各实施方式。只要可能,在所有附图中使用相同的附图标记来表示相同或类似的特征。
在本文中,根据光伏电池的结构,术语“基板”可以用来描述基板或者覆板(superstrate)。例如,如果当所述基板在组装入光伏电池的时候,位于光伏电池的光入射侧,则所述基板是覆板。所述覆板可以为光伏材料提供保护,使其免受冲击和环境降解,同时允许太阳光谱中合适的波长透过。另外,可以将多个光伏电池组装成光伏模块。
在本文中,术语“相邻的”可以定义为紧邻。相邻的结构可以互相物理接触,也可以不发生物理接触。相邻的结构可以包括设置在它们之间的其它的层以及/或者结构。
在本文中,术语“平面的”可以定义为具有基本上形态平坦的表面。
尽管在实施方式中描述了示例性的数值范围,但是各个范围可以包括由各个范围的端点组成的范围内的任意小数位的数值。
在本发明中,示例性组合物的多价组分包括,例如Fe2O3,SnO2,As2O5,Sb2O5。这些材料可以以所述氧化物的形式配制,但是也可以以混合价态或者其他价态的形式配制。
一个实施方式是一种玻璃,其包含:
60-65摩尔%的SiO2;
8-12摩尔%的Al2O3;
7-15摩尔%的B2O3;
大于0摩尔%至8摩尔%的M2O;
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
另一个实施方式是一种玻璃,其包含:
61-64摩尔%的SiO2;
8-12摩尔%的Al2O3;
9-15摩尔%的B2O3;
大于0摩尔%至4摩尔%的M2O;
12-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
另一个实施方式是一种玻璃,其包含:
60-65摩尔%的SiO2;
8摩尔%至小于10摩尔%的Al2O3;
大于11摩尔%至15摩尔%的B2O3;
大于0摩尔%至小于1摩尔%的M2O;
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
另一个实施方式是一种玻璃,其包含:
60-65摩尔%的SiO2;
10-12摩尔%的Al2O3;
7-11摩尔%的B2O3;
1-8摩尔%的M2O;以及
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
在一个实施方式中,M是选自以下的碱金属:Li,Na,K,Rb,Cs,以及它们的组合。在一些实施方式中,M选自Li,K,Cs,以及它们的组合。
在一个实施方式中,R选自Mg,Ca,Dr,Ba,以及它们的组合。在一些实施方式中,R选自Mg,Ca,Sr,以及它们的组合。
根据另一个实施方式,所述玻璃基本不含BaO。例如,BaO的含量可以等于或小于0.05摩尔%,例如为0摩尔%。
在一些实施方式中,所述玻璃基本不含Sb2O3,As2O3,或其组合,例如,所述玻璃包含等于或小于0.05摩尔%的Sb2O3或As2O3或其组合。例如,所述玻璃可以包含0摩尔%的Sb2O3或As2O3或其组合。
在一些实施方式中,所述玻璃包含60-65摩尔%的SiO2。在一些实施方式中,所述玻璃包含61-64摩尔%的SiO2。在一些实施方式中,所述玻璃包含62-64摩尔%的SiO2。
在一些实施方式中,所述玻璃包含0.01-0.4摩尔%的SnO2。
根据一个实施方式的玻璃包含:
62-65摩尔%的SiO2;
10-12摩尔%的Al2O3;
7-11摩尔%的B2O3;
3-8摩尔%的MgO;
3-10摩尔%的CaO;
3-8摩尔%的SrO;以及
1-8摩尔%的M2O;
其中,M是选自K,Na,及其组合的碱金属,CaO/(CaO+SrO)为0.4-1。
在一个实施方式中,所述玻璃是可卷起的。在一个实施方式中,所述玻璃是可下拉的。例如,所述玻璃可以狭缝拉制或熔合拉制。根据另一个实施方式,所述玻璃可以通过浮法成形。
所述玻璃还可以包含等于或小于2摩尔%的TiO2,MnO,ZnO,Nb2O5,MoO3,Ta2O5,WO3,ZrO2,Y2O3,La2O3,HfO2,CdO,SnO2,Fe2O3,CeO2,As2O3,Sb2O3,Cl,Br,P2O5,或其组合。
如上所述,根据一些实施方式,所述玻璃包含7-15摩尔%,例如7-11摩尔%的B2O3。相对于不含B2O3的玻璃,通过向玻璃中加入B2O3可以降低熔融温度,降低液相线温度,增大液相线粘度,改进机械耐久性。
如上所述,根据一些实施方式,所述玻璃包含9-15摩尔%的RO,其中R是碱土金属。所述玻璃可以包含例如1-8摩尔%的MgO。可以将MgO加入玻璃中,以降低熔融温度和增大应变点。相对于其它的碱土金属(例如CaO,SrO,BaO),加入MgO会不利地降低CTE,可以采取其它的调节将CTE保持在所需的范围内。合适的调节的例子包括减少CaO的同时增加SrO,增大碱金属氧化物的浓度,用较大的碱金属氧化物(例如K2O)完全或部分地代替较小的碱金属氧化物(例如Na2O)。
在一些实施方式中,所述玻璃包含1-9摩尔%的CaO。相对于碱金属氧化物或者SrO,CaO贡献较高的应变点,较低的密度和较低的熔融温度。其为某些可能的失透相的主要组分,特别是钙长石(CaAl2Si2O8),该相包含与类似的钠相、钠长石(NaAlSi3O8)的完全固溶体。单单高Na含量和高Ca含量会导致出现无法接受的高液相线温度。但是,用于CaO的化学来源包括石灰石,这是一种非常廉价的材料,因此在高体积和低成本主导的情况下,通常可以使得CaO含量相对于其他碱土金属氧化物含量在合理的情况下尽可能高。
在一些实施方式中,所述玻璃可包含0-5摩尔%的SrO。在某些实施方式中,所述玻璃不含有意配入的SrO,当然,SrO也可以作为其他批料中的污染组分包含在其中。SrO贡献了较高的热膨胀系数,可以通过控制SrO和CaO的相对比例来改进液相线温度,由此改进液相线粘度。SrO不能像CaO或MgO那样有效地用来改进应变点,用SrO代替此二者中的任一种都会使得熔融温度升高。
在某些实施方式中,所述玻璃满足以下表达式中的一个或多个:
1.0≤(M2O+RO)/Al2O3≤2;和
0.4≤CaO/(CaO+SrO)≤1。
(M2O+RO)/Al2O3的比例优选大于1.0,以便在初始熔融步骤中促进从玻璃中除去气泡。之所以发生这种情况,是因为没有参与Al2O3稳定化的碱金属和碱土金属氧化物会用来消化氧化硅源,通常是商品砂。因此,在熔融的早期除去了可能成为气泡成核和生长的位点的表面区域,获得了相对无气泡的玻璃。
CaO/(CaO+SrO)的比值优选在0.4至1之间,以便使得液相线温度(因此液相线粘度)和熔融温度之间获得良好的平衡。例如,具有低碱金属浓度和高SrO浓度的组合物具有较高的熔融温度,如果SrO过高,则相对于包含较多碱金属氧化物和较低SrO的玻璃,液相线温度会升高。但是,在所有其它的组分浓度固定的情况下,当CaO/(CaO+SrO)比值为0.4-1的时候,液相线温度经常获得局部的最小值。
同样如上文所述,根据一些实施方式,所述玻璃包含大于0摩尔%至8摩尔%的M2O,例如0.05-8摩尔%的M2O,0.1-8摩尔%的M2O,0.5-8摩尔%的M2O,1-8摩尔%的M2O,其中M是一种或多种碱金属阳离子Li,Na,K,Rb和Cs。在某些实施方式中,需要所述碱金属是Li,K和Cs,或其组合。碱金属阳离子会使得CTE急剧升高,但是也会降低应变点,并且根据其加入形式,会使得熔融温度升高。对CTE效果最低的碱金属氧化物是Li2O,效果最高的碱金属氧化物是Cs2O。如上文所述,钠可以参与到本发明玻璃的一种可能的失透相中,尽管可以对其他组分进行调节来抵消此种现象,例如改变CaO/(CaO+SrO)比值,但是此种趋势使得优选用其它的碱金属代替钠,或者使用碱金属的混合物代替单独使用的钠。如果大体积和低成本是很重要的,那么优选尽可能将所述碱金属氧化物限定为Na2O和K2O,或其组合。
根据一些实施方式,所述玻璃还可以包含很多种其它的组分。例如,所述玻璃可以包含SnO2,Fe2O3,MnO,CeO2,As2O3,Sb2O3,Cl,Br,或其组合。这些材料可以作为澄清剂(例如,用来促进从用于制造玻璃的熔融批料除去气态夹杂物)和/或其他目的加入。在某些实施方式中,所述玻璃包含SnO2(例如,以氧化物的摩尔百分数计,0.02-0.3摩尔%的SnO2,等)和Fe2O3(例如,以氧化物的摩尔百分数计,0.005-0.08摩尔%的Fe2O3,0.01-0.08摩尔%的Fe2O3,等)。例如,在某些实施方式中,所述玻璃包含SnO2和Fe2O3,其中,以氧化物的摩尔百分数计:
0.02≤SnO2≤0.3;且
0.005≤Fe2O3≤0.08。
在某些实施方式中,所述玻璃包含小于0.05摩尔%的Sb2O3,As2O3,或其组合。在某些实施方式中,所述玻璃包含SnO2,Fe2O3,CeO2,Cl,Br,或其组合,包含小于0.05摩尔%(例如小于0.04摩尔%,小于0.03摩尔%,小于0.02摩尔%,小于0.01摩尔%等)的Sb2O3,As2O3,或其组合。在某些实施方式中,所述玻璃包含SnO2和Fe2O3,包含小于0.05摩尔%(例如小于0.04摩尔%,小于0.03摩尔%,小于0.02摩尔%,小于0.01摩尔%等)的Sb2O3,As2O3,或其组合。在某些实施方式中,所述玻璃包含SnO2和Fe2O3,其中,以氧化物的摩尔百分数计:
0.02≤SnO2≤0.3;且
0.005≤Fe2O3≤0.08,
包含小于0.05摩尔%的Sb2O3,As2O3,或其组合。
根据一些实施方式,所述玻璃(例如任意上文讨论的玻璃)可以包含F,Cl或Br,例如,玻璃包含Cl和/或Br作为澄清剂。例如,以摩尔百分数计,所述玻璃可以包含氟、氯和/或溴,其中:F+Cl+Br≤0.4,例如F+Cl+Br≤0.3,F+Cl+Br≤0.2,F+Cl+Br≤0.1,0.001≤F+Cl+Br≤0.4,和/或0.005≤F+Cl+Br≤0.4。例如,在某些实施方式中,所述玻璃包含SnO2和Fe2O3以及任选的氟、氯和/或溴,使得以氧化物的摩尔百分数计:0.02≤SnO2≤0.3,0.005≤Fe2O3≤0.08和F+Cl+Br≤0.4;在某些实施方式中,所述玻璃包含SnO2和Fe2O3以及任选的Sb2O3,As2O3,氟,氯和/或溴,使得以氧化物的摩尔百分数计,0.02≤SnO2≤0.3,0.005≤Fe2O3≤0.08,且F+Cl+Br≤0.4,并且使得玻璃包含小于0.05摩尔%(例如小于0.04摩尔%,小于0.03摩尔%,小于0.02摩尔%,小于0.01摩尔%等)的Sb2O3,As2O3,或其组合。
根据一些实施方式,所述玻璃包含BaO。在某些实施方式中,所述玻璃包含小于0.1摩尔%的BaO。
根据一些实施方式,所述玻璃还可以包含商业制备的玻璃中通常会出现的污染物。作为附加或者替代,可以加入各种其它的氧化物(例如TiO2,MnO,ZnO,Nb2O5,MoO3,Ta2O5,WO3,ZrO2,Y2O3,La2O3,P2O5,等等),尽管对其它的玻璃组分进行了调整,但是不会使得它们的熔融特性或者成形特性变差。根据一些实施方式,在这些情况下,所述玻璃还包含其它的氧化物,这些其它的氧化物的含量通常不超过2摩尔%,它们的总浓度通常小于或等于5摩尔%,但是也可以使用更高的量,只要使用的量不会使得组成处于上述范围之外即可。根据一些实施方式,所述玻璃还包含与批料相关的污染物和/或由制备玻璃所用的熔融、澄清和/或成形设备引入的污染物(如ZrO2)。
根据一些实施方式,所述玻璃可以进行下拉操作;也即是说,能够采用下拉法将玻璃成形制成片材,所述下拉法包括例如但不限于熔合拉制法和狭缝拉制法,这些方法是玻璃制造领域技术人员已知的。这些下拉工艺被用于显示器玻璃或可离子交换玻璃之类的平板玻璃的大规模制造。
所述熔合拉制法使用等压槽(isopipe),该等压槽包括沟槽,用来接受熔融的玻璃原料。这些沟槽具有堰,这些堰沿着沟槽的长度,在沟槽的两侧在顶部开放。当在沟槽内装入熔融材料的时候,熔融的玻璃从堰上溢流。在重力的作用下,熔融玻璃从等压槽的外表面流下。这些外表面向下和向内延伸,使得它们在拉制容器下方的边缘处结合。两个流动玻璃的表面在此边缘处结合并熔合起来,形成单独的流动片材。所述熔合下拉法的优点在于,由于从沟槽溢流的两个玻璃膜会熔合在一起,因此制得的玻璃片的任一外表面都没有与设备的任意部件相接触。因此,所述接触不会影响表面性质。
狭缝拉制法与熔合拉制法不同。在此方法中,将熔融的原料玻璃提供给管道。管道的底部具有开放的狭缝,其一个维度的尺寸比另一个维度的尺寸宽,包括沿着狭缝的长度延伸的喷嘴。熔融的玻璃流过所述狭缝/喷嘴,以连续的片材的形式通过该狭缝/喷嘴下拉,并进入退火区。相较于熔合拉制法,所述狭缝拉制法提供了更薄的片材,这是因为通过狭缝仅仅拉制了单个片材,而不是像熔合下拉法那样形成了熔合在一起的两个片材。
为了能够适应下拉工艺,本发明所述的铝硼硅酸盐玻璃具有高液相线粘度。在一个实施方式中,所述玻璃的液相线粘度等于或大于50,000泊,例如等于或大于150,000泊,例如等于或大于500,000泊。所述玻璃的液相线粘度与液相线温度和软化点之间的差异极为密切地相关。图1中的直线10显示了此种关系。对于下拉法,玻璃的液相线-软化点优选约低于230℃,更优选低于200℃。
因此,在一个实施方式中,所述玻璃的应变点等于或高于600℃,例如等于或高于620℃。在一些实施方式中,所述玻璃的热膨胀系数等于或大于38×10-7,例如等于或大于40×10-7,例如等于或大于45×10-7。
根据一个实施方式,所述玻璃的应变点可以等于或高于620℃并且/或者热膨胀系数等于或大于45×10-7。
根据一个实施方式,所述玻璃在包含一种或多种碱金属离子盐的盐浴中进行离子交换。可以对玻璃进行离子交换以改变其机械性质。例如,较小的碱金属离子,例如锂或钠可以在包含一种或多种较大的碱金属离子(例如钠、钾、铷或铯)的熔融盐中进行离子交换。如果在远低于应变点的温度下进行足够的时间,将会形成扩散曲线,其较大的碱金属从盐浴移动入玻璃表面中,较小的离子从玻璃的内部移动到盐浴中。当将样品取出的时候,表面会发生压缩,产生提高的韧性,使其免于受到破坏。当玻璃将要经受不利的环境条件,例如光伏栅格受到冰雹袭击的时候,所述韧性是人们所需要的。玻璃中已有的大的碱金属也可能被盐浴中较小的碱金属交换。如果在接近应变点的温度下进行,如果将玻璃取出,并且将玻璃的表面快速再次加热至高温,然后快速冷却,则会由于热回火,在玻璃的表面产生显著的压缩应力。这也可以提供保护,以免受到环境条件的破坏。本领域技术人员很清楚,任何单价阳离子均可以用来交换玻璃中已有的碱金属,包括铜,银,铊等,还可以提供用于最终应用的具有潜在价值的性质,例如为发射的光产生颜色,或者提供具有增大的折射率的层,用于俘获光。
根据另一个实施方式,可以通过浮法形成玻璃领域已知的方式,通过浮法对玻璃成形。
在一个实施方式中,所述玻璃是片材的形式。所述片材形式的玻璃可以进行热回火。
在一个实施方式中,有机发光二极管器件包含片材形式的玻璃。
在一个实施方式中,所述光伏器件包含片材形式的玻璃。所述光伏器件可以包含超过一个的玻璃片,例如作为基板和/或覆板。在一个实施方式中,所述玻璃片基本上是平面状的。根据一个实施方式,所述玻璃片是透明的。
根据一些实施方式,所述玻璃片的厚度等于或小于4.0毫米,例如等于或小于3.5毫米,例如等于或小于3.2毫米,例如等于或小于3.0毫米,例如等于或小于2.5毫米,例如等于或小于2.0毫米,例如等于或小于1.9毫米,例如等于或小于1.8毫米,例如等于或小于1.5毫米,例如等于或小于1.1毫米,例如0.5-2.0毫米,例如0.5-1.1毫米,例如0.7-1.1毫米。尽管有一些示例性的厚度,但是玻璃片的厚度可以包括0.1毫米至最高达4.0毫米(包括4.0毫米)范围内任意小数的数值。
在另一个实施方式中,所述光伏器件包括玻璃片以及与所述玻璃片相邻的活性光伏介质。
所述活性光伏介质可以包含多个层,例如无定形硅层和微晶硅层。
在一个实施方式中,所述活性光伏介质包含碲化镉,二硒化铜铟镓,无定形硅,晶体硅,微晶硅,或者它们的组合。
图2所示的另一个实施方式包括一种光伏器件200,其包括玻璃片12和与该玻璃片相邻的活性光伏介质16,所述玻璃片12包含任意上述的玻璃组合物,所述活性光伏介质包含碲化镉。根据一个实施方式,所述玻璃片具有前文所述的厚度。所述光伏器件还可以包括导电层14,例如与玻璃片相邻或者设置在玻璃片上的透明导电氧化物。
在一个实施方式中,电致变色器件包括片材形式的玻璃。所述电致变色器件可以是例如,电致变色窗。
实施例
以下显示了根据本发明一个实施方式的制造本发明示例性玻璃的样品,如表1所示。该组成对应于表7所示的组成编号46。
氧化物 | 摩尔% |
SiO2 | 63.5 |
Al2O3 | 10.7 |
B2O3 | 10.3 |
K2O | 2.3 |
MgO | 4.4 |
CaO | 5.2 |
SrO | 3.5 |
SnO2 | 0.1 |
表1
在一些实施方式中,总量之和不是100%,因为会以无法忽略的浓度存在某些不确定的元素。
如表2所示称取批料,加入4升的塑料容器中:
批料组分 | 批料重量 |
砂子 | 1713.42 |
氧化铝 | 486.27 |
硼酸 | 570.42 |
碳酸钾 | 143.05 |
氧化镁 | 78.62 |
石灰石 | 240.73 |
碳酸锶 | 234.23 |
10%SnO2和90%砂子 | 6.92 |
表2
应当注意,根据来源,在批料中,石灰石可以包含不确定的元素和/或各种量的一种或多种氧化物,例如MgO和/或BaO。砂子中优选至少80质量%可以通过60目的筛网,例如80目,例如100目。在此实施例中,加入的SnO2以10重量%的水平与砂子预先混合,以确保与其他组分均一混合。将装有批料的瓶子安装在滚筒上,对批料进行混合,由此制得均一的批料,将柔软的聚集物打碎。将混合的批料转移到1800cc的铂坩锅中,放入高温陶瓷支架中。将位于支架中的铂坩锅放入保持在1550℃的glo-bar加热炉内。6小时之后,取出所述坩锅和支架,将玻璃熔体倒在冷的表面上,例如倒在钢板上,形成圆片,然后转移到保持在670℃的退火器中。所述玻璃圆片在退火器温度下保持2小时,然后以1℃/分钟的速率冷却至室温。
表3,表4,表5,表6,表7和表8显示了根据本发明实施方式的示例性的玻璃,这些玻璃根据以上实施例制备。一些玻璃的性质数据也显示于表3,表4,表5,表6,表7和表8中。
表8所示的玻璃49具有低的液相线温度(940℃),因此具有超过5,000,000泊的极高的液相线粘度,这种玻璃是一种优选的用于各种用途的玻璃,例如用于光伏装置的玻璃。表8所示的示例性的玻璃包含:
62-64摩尔%的SiO2;
8-12摩尔%的Al2O3;
9-15摩尔%的B2O3;
大于0摩尔%至4摩尔%的M2O;
12-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
另外,表8所示的玻璃的退火点≥640℃,热膨胀系数(CTE)为40-50×10-7/℃,200泊的温度≤1550℃,液相线粘度≥500,000泊。液相线粘度可能取决于K2O含量,例如与示例性的玻璃48、50和51相比,示例性的玻璃49具有中等K2O含量,其具有超过5,000,000泊的最大的液相线粘度值。
表3.
表4.
表5.
重量百分数 | 玻璃 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
SiO2 | 56.19 | 56.33 | 56.46 | 56.6 | 56.72 | 56.48 | 57.32 | 58.17 | 57.29 | 56.92 | |
Al2O3 | 17.45 | 17.01 | 16.56 | 16.11 | 15.66 | 17.77 | 17.52 | 17.27 | 17.03 | 16.63 | |
B2O3 | 11.27 | 10.63 | 9.98 | 9.33 | 8.68 | 11.17 | 9.70 | 8.21 | 9.26 | 9.38 |
MgO | 2.78 | 2.61 | 2.43 | 2.26 | 2.08 | 2.76 | 2.39 | 2.01 | 2.27 | 2.29 | |
CaO | 4.62 | 4.36 | 4.10 | 3.84 | 3.58 | 4.57 | 3.94 | 3.31 | 3.77 | 3.84 | |
SrO | 5.83 | 5.52 | 5.20 | 4.89 | 4.57 | 5.76 | 5.00 | 4.23 | 4.79 | 4.88 | |
BaO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
Na2O | 1.68 | 3.37 | 5.06 | 6.77 | 8.48 | 1.30 | 3.92 | 6.56 | 5.39 | 5.86 | |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
SnO2 | 0.18 | 0.18 | 0.21 | 0.21 | 0.23 | 0.18 | 0.20 | 0.23 | 0.21 | 0.21 | |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
总计 | 100 | 100.01 | 100 | 100.01 | 100 | 99.99 | 99.99 | 99.99 | 100.01 | 100.01 | |
摩尔百分数 | 玻璃 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
SiO2 | 62.18 | 62.16 | 62.14 | 62.12 | 62.10 | 62.56 | 63.28 | 64.00 | 63.08 | 62.60 | |
Al2O3 | 11.38 | 11.06 | 10.74 | 10.42 | 10.10 | 11.60 | 11.40 | 11.20 | 11.05 | 10.78 | |
B2O3 | 10.76 | 10.12 | 9.48 | 8.84 | 8.20 | 10.68 | 9.24 | 7.80 | 8.80 | 8.90 | |
MgO | 4.58 | 4.29 | 3.99 | 3.70 | 3.40 | 4.56 | 3.93 | 3.30 | 3.72 | 3.75 | |
CaO | 5.48 | 5.16 | 4.84 | 4.52 | 4.20 | 5.42 | 4.66 | 3.90 | 4.45 | 4.52 | |
SrO | 3.74 | 3.53 | 3.32 | 3.11 | 2.90 | 3.70 | 3.20 | 2.70 | 3.06 | 3.11 | |
BaO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
Na2O | 1.80 | 3.60 | 5.40 | 7.20 | 9.00 | 1.40 | 4.20 | 7.00 | 5.75 | 6.25 | |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
SnO2 | 0.08 | 0.08 | 0.09 | 0.09 | 0.10 | 0.08 | 0.09 | 0.10 | 0.09 | 0.09 | |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
总计 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
性质 | 玻璃 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
应变点 | 611 | 590 | 578 | 565 | 620 | 589 | 577 | 577 | 576 | ||
退火温度 | 659 | 636 | 622 | 607 | 670 | 635 | 623 | 625 | 621 | ||
软化点 | 887.1 | 856.5 | 831.1 | 807.2 | 780 | 899.5 | 866.3 | 850.5 | 843 | 836.1 | |
CTE | 41.6 | 47.7 | 53.9 | 59.6 | 40.4 | 48.1 | 56.6 | 52.8 | 55.4 | ||
密度 | 2.478 | 2.48 | 2.492 | 2.494 | 2.501 | 2.472 | 2.467 | 2.463 | 2.472 | 2.478 | |
粘度 | 玻璃 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
A | -2.475 | -2.209 | -2.175 | -2.086 | -1.813 | -2.817 | -2.501 | -1.845 |
B | 5764.2 | 5523.2 | 5563.1 | 5506.2 | 4988.5 | 6843.6 | 6402.1 | 5180.5 | |||
To | 306 | 290.2 | 258.9 | 231 | 242.7 | 193.3 | 197.4 | 272 | |||
200 | 1512.9 | 1514.85 | 1501.76 | 1486.11 | 1455.26 | 1530.46 | 1530.61 | 1521.51 | |||
3000 | 1274.43 | 1261.55 | 1243.15 | 1220.77 | 1185.68 | 1280.6 | 1268.32 | 1245.39 | |||
30000 | 1135.13 | 1116.27 | 1095.19 | 1069.96 | 1035.77 | 1131.54 | 1114.85 | 1091.42 | |||
50000 | 1109.49 | 1089.74 | 1068.2 | 1042.53 | 1008.75 | 1103.84 | 1086.58 | 1063.64 | |||
液相线 | 玻璃 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
内部 | 1010 | 1025 | 1040 | 1020 | 980 | 1030 | 1020 | 1070 | 1010 | 1040 | |
液相线粘度 | 516159.7 | 203050.1 | 88539.17 | 78110.11 | 89722.76 | 238527.3 | 79513.84 | ||||
内部液-软 | 122.9 | 168.5 | 208.9 | 212.8 | 200 | 130.5 | 153.7 | 219.5 | 167 | 203.9 |
表6.
重量百分数 | 玻璃 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 |
SiO2 | 56.76 | 57.00 | 57.33 | 57.72 | 58.11 | 59.01 | 56.88 | 57.06 | 57.30 | |
Al2O3 | 17.19 | 16.95 | 17.52 | 17.64 | 17.76 | 15.66 | 17.09 | 16.32 | 17.52 | |
B2O3 | 10.19 | 9.6 | 9.66 | 9.72 | 9.79 | 9.84 | 10.20 | 10.72 | 9.70 | |
MgO | 2.50 | 2.35 | 2.37 | 2.81 | 3.26 | 2.45 | 2.56 | 2.65 | 2.39 | |
CaO | 4.17 | 3.92 | 3.97 | 4.00 | 4.03 | 4.01 | 4.15 | 4.36 | 3.94 | |
SrO | 5.24 | 4.98 | 5.00 | 3.93 | 2.85 | 5.04 | 5.16 | 5.42 | 5.00 | |
BaO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
Na2O | 3.74 | 4.99 | 3.92 | 3.95 | 3.98 | 3.77 | 3.74 | 0 | 3.92 | |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 3.24 | 0 | |
SnO2 | 0.20 | 0.20 | 0.23 | 0.23 | 0.23 | 0.23 | 0.23 | 0.23 | 0.23 | |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
总计 | 99.99 | 99.99 | 100 | 100 | 100.01 | 100.01 | 100.01 | 100 | 100 | |
摩尔百分数 | 玻璃 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 |
SiO2 | 62.63 | 62.78 | 63.3 | 63.3 | 63.30 | 64.6 | 62.7 | 63.50 | 63.28 |
Al2O3 | 11.18 | 11.00 | 11.40 | 11.40 | 11.40 | 10.10 | 11.10 | 10.70 | 11.40 | |
B2O3 | 9.70 | 9.13 | 9.20 | 9.20 | 9.20 | 9.30 | 9.70 | 10.30 | 9.24 | |
MgO | 4.12 | 3.86 | 3.90 | 4.60 | 5.30 | 4.00 | 4.20 | 4.40 | 3.93 | |
CaO | 4.93 | 4.63 | 4.70 | 4.70 | 4.70 | 4.70 | 4.90 | 5.20 | 4.66 | |
SrO | 3.35 | 3.18 | 3.20 | 2.50 | 1.80 | 3.20 | 3.30 | 3.50 | 3.20 | |
BaO | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
Na2O | 4.00 | 5.33 | 4.20 | 4.20 | 4.20 | 4.00 | 4.00 | 0.00 | 4.20 | |
K2O | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2.3 | 0 | |
SnO2 | 0.09 | 0.09 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | |
Fe2O3 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
总计 | ||||||||||
性质 | 玻璃 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 |
应变点 | 589 | 578 | 596 | 597 | 596 | 590 | 593 | 619 | 597 | |
退火温度 | 638 | 626 | 643 | 644 | 645 | 637 | 640 | 669 | 645 | |
软化点 | 858.5 | 843.2 | 867.6 | 867 | 876.9 | 859.5 | 858.5 | 898 | 873 | |
CTE | 48.4 | 51.7 | 48.1 | 47.3 | 46.1 | 47.6 | 48 | 44.2 | 47.2 | |
密度 | 2.477 | 2.474 | 2.475 | 2.466 | 2.451 | 2.472 | 2.476 | 2.465 | 2.466 | |
粘度 | 玻璃 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 |
A | -2.549 | -2.625 | -2.625 | -2.567 | ||||||
B | 6218.5 | 6434.5 | 6434.5 | 6097.1 | ||||||
To | 233.8 | 223.8 | 223.8 | 303.3 | ||||||
200 | 1515.96 | 1530.02 | 1530.02 | 1555.78 | ||||||
3000 | 1265.72 | 1278.27 | 1278.27 | 1312.07 | ||||||
30000 | 1118.85 | 1129.8 | 1129.8 | 1168.86 | ||||||
50000 | 1091.76 | 1102.35 | 1102.35 | 1142.43 | ||||||
液相线 | 玻璃 | 39 | 40 | 41 | 42 | 43 | 44 | 45 | 46 | 47 |
内部 | 1045 | 1040 | 1095 | 1080 | 1060 | 1015 | 1060 | 1050 | 1065 | |
液相线粘度 | 130859 | 181336.2 | 321798.1 | 396638.1 | ||||||
内部液-软 | 186.5 | 196.8 | 227.4 | 213 | 183.1 | 155.5 | 201.5 | 152 | 192 |
表7.
摩尔百分数 | 玻璃 | 48 | 49 | 50 | 51 |
SiO2 | 63 | 62.95 | 62.9 | 62.85 | |
Al2O3 | 11 | 10.3 | 9.65 | 9 | |
B2O3 | 10.2 | 11.6 | 13.05 | 14.5 | |
MgO | 5.5 | 4.13 | 2.75 | 1.38 | |
CaO | 6.1 | 4.6 | 3.05 | 1.53 | |
SrO | 1.8 | 1.43 | 1.05 | 1.68 | |
BaO | 0 | 3.1 | 6.15 | 9.22 | |
K2O | 2.4 | 1.8 | 1.2 | 0.6 | |
SnO2 | 0.1 | 0.1 | 0.1 | 0.1 | |
重量百分数 | 玻璃 | 48 | 49 | 50 | 51 |
SiO2 | 57.2 | 54.9 | 52.9 | 51 | |
Al2O3 | 16.9 | 15.3 | 13.8 | 12.4 | |
B2O3 | 10.7 | 11.7 | 12.7 | 13.6 | |
MgO | 3.34 | 2.42 | 1.55 | 0.75 | |
CaO | 5.17 | 3.74 | 2.4 | 1.16 | |
SrO | 2.81 | 2.16 | 1.53 | 0.95 | |
BaO | 0 | 6.91 | 13.2 | 19.1 | |
K2O | 3.41 | 2.47 | 1.58 | 0.76 |
SnO2 | 0.23 | 0.22 | 0.21 | 0.2 | |
性质 | 玻璃 | 48 | 49 | 50 | 51 |
应变点 | 628 | 609 | 603 | 598 | |
退火温度 | 678 | 659 | 651 | 644 | |
软化点 | 909 | 890 | 876 | 858 | |
CTE | 42.8 | 43.9 | 45.4 | 46 | |
密度 | 2.44 | 2.516 | 2.606 | 2.677 | |
粘度 | 玻璃 | 48 | 49 | 50 | 51 |
200 | 1529 | 1525 | 1528 | ||
内部液相 | 1020 | 940 | 980 | 980 | |
液相线粘度 | 822,000 | 5,233,000 | 1,100,000 |
表8.
根据本发明的含碱金属的玻璃相对于无碱金属的替代品具有低的熔融温度,并且具有快的熔融速率,因此可以进行高体积、低成本的熔融和成形,同时保持有竞争力的性质,包括在再加热到高温的时候具有特定的机械和尺寸稳定性。这些玻璃非常适合用于大体积片状玻璃用途,特别是OLED照明和碲化镉(CdTe)光伏器件,这些用途需要热稳定性、大体积和低成本的基板性质。
对本领域的技术人员而言,显而易见的是,可以在不偏离本发明的精神或范围的情况下对本发明进行各种修改和变动。因此,本发明意图是覆盖本发明的修改和变动,只要这些修改和变动在所附权利要求及其等同方案的范围之内即可。
Claims (32)
1.一种玻璃,包含:
60-65摩尔%的SiO2;
8-12摩尔%的Al2O3;
7-15摩尔%的B2O3;
大于0摩尔%至8摩尔%的M2O;
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
2.如权利要求1所述的玻璃,其特征在于,所述玻璃包含0.05摩尔%的M2O。
3.如权利要求1所述的玻璃,其特征在于,所述玻璃包含0.1摩尔%的M2O。
4.如权利要求1所述的玻璃,其特征在于,所述玻璃包含:
61-64摩尔%的SiO2;
8-12摩尔%的Al2O3;
9-15摩尔%的B2O3;
大于0摩尔%至4摩尔%的M2O;
12-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
5.如权利要求1所述的玻璃,其特征在于,所述玻璃包含:
60-65摩尔%的SiO2;
8摩尔%至小于10摩尔%的Al2O3;
大于11摩尔%至15摩尔%的B2O3;
大于0摩尔%至小于1摩尔%的M2O;
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
6.如权利要求1所述的玻璃,其特征在于,所述玻璃包含:
60-65摩尔%的SiO2;
10-12摩尔%的Al2O3;
7-11摩尔%的B2O3;
1-8摩尔%的M2O;以及
9-15摩尔%的RO;
其中,M是碱金属,R是碱土金属。
7.如权利要求1所述的玻璃,其特征在于,M选自Li,Na,K,Rb,Cs,以及它们的组合。
8.如权利要求7所述的玻璃,其特征在于,M选自Li,K,Cs,以及它们的组合。
9.如权利要求1所述的玻璃,其特征在于,R选自Mg,Ca,Sr,Ba,以及它们的组合。
10.如权利要求9所述的玻璃,其特征在于,R选自Mg,Ca,Sr,以及它们的组合。
11.如权利要求1所述的玻璃,其特征在于,所述玻璃包含62-65%的SiO2。
12.如权利要求1所述的玻璃,其特征在于,所述玻璃还包含0.01-0.4%的SnO2。
13.如权利要求1所述的玻璃,其特征在于,所述玻璃包含:
62-65%的SiO2;
10-12%的Al2O3;
7-11%的B2O3;
3-8%的MgO;
3-10%的CaO;
3-8%的SrO;以及
1-8%的M2O;
其中,M是选自K,Na,及其组合的碱金属,CaO/(CaO+SrO)为0.4-1。
14.如权利要求1所述的玻璃,其特征在于,所述玻璃是可以下拉的。
15.如权利要求1所述的玻璃,其特征在于,所述玻璃是狭缝拉制或者熔合拉制的。
16.如权利要求1所述的玻璃,其特征在于,所述玻璃是浮法成形的。
17.如权利要求1所述的玻璃,其特征在于,所述玻璃基本不含BaO。
18.如权利要求1所述的玻璃,其特征在于,所述玻璃基本不含Sb2O3,As2O3,或其组合。
19.如权利要求1所述的玻璃,其特征在于,所述玻璃在包含一种或多种碱金属离子的盐的盐浴中进行离子交换。
20.如权利要求1所述的玻璃,其特征在于,所述玻璃还包含等于或小于2摩尔%的TiO2,MnO,ZnO,Nb2O5,MoO3,Ta2O5,WO3,ZrO2,Y2O3,La2O3,P2O5,或其组合。
21.如权利要求1所述的玻璃,其特征在于,所述玻璃是片材的形式。
22.如权利要求21所述的玻璃,其特征在于,所述玻璃是热回火的。
23.一种有机发光二极管器件,其包含权利要求21所述的玻璃。
24.一种光伏器件,其包含权利要求21所述的玻璃。
25.如权利要求24所述的光伏器件,其特征在于,所述光伏器件还包括与所述玻璃相邻的活性光伏介质。
26.如权利要求25所述的光伏器件,其特征在于,所述活性光伏介质包含碲化镉,二硒化铜铟镓,无定形硅,晶体硅,微晶硅,或者它们的组合。
27.如权利要求1所述的玻璃,其特征在于,所述玻璃的应变点等于或高于600℃。
28.如权利要求1所述的玻璃,其特征在于,所述玻璃的热膨胀系数等于或大于38×10-7。
29.如权利要求1所述的玻璃,其特征在于,所述玻璃的热膨胀系数等于或大于45×10-7。
30.如权利要求1所述的玻璃,其特征在于,所述玻璃的应变点等于或高于620℃并且热膨胀系数等于或大于45×10-7。
31.如权利要求1所述的玻璃,其特征在于,所述玻璃的液相线粘度等于或大于50,000泊。
32.如权利要求31所述的玻璃,其特征在于,所述玻璃的液相线粘度等于或大于150,000泊。
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US12/573,213 US8445394B2 (en) | 2008-10-06 | 2009-10-05 | Intermediate thermal expansion coefficient glass |
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2009
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- 2009-10-06 JP JP2011531105A patent/JP6042613B2/ja active Active
- 2009-10-06 KR KR1020167021282A patent/KR20160097385A/ko active Application Filing
- 2009-10-06 CN CN2009801404052A patent/CN102171154A/zh active Pending
- 2009-10-06 MX MX2011003630A patent/MX2011003630A/es unknown
- 2009-10-06 KR KR1020177030788A patent/KR101891459B1/ko active IP Right Grant
- 2009-10-06 KR KR1020117010301A patent/KR101647526B1/ko active IP Right Grant
- 2009-10-06 CA CA2739098A patent/CA2739098A1/en not_active Abandoned
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EP2349938B1 (en) | 2018-02-21 |
US20160145146A1 (en) | 2016-05-26 |
TWI403482B (zh) | 2013-08-01 |
WO2010042460A3 (en) | 2010-06-03 |
US8445394B2 (en) | 2013-05-21 |
EP2349938A2 (en) | 2011-08-03 |
KR20170121338A (ko) | 2017-11-01 |
KR20160097385A (ko) | 2016-08-17 |
TW201022174A (en) | 2010-06-16 |
RU2011118352A (ru) | 2012-11-20 |
US9266769B2 (en) | 2016-02-23 |
WO2010042460A2 (en) | 2010-04-15 |
JP2012504548A (ja) | 2012-02-23 |
AU2009302561A1 (en) | 2010-04-15 |
JP5883174B2 (ja) | 2016-03-09 |
MX2011003630A (es) | 2011-05-31 |
JP2015164893A (ja) | 2015-09-17 |
KR101647526B1 (ko) | 2016-08-10 |
US20130255779A1 (en) | 2013-10-03 |
JP6417531B2 (ja) | 2018-11-07 |
JP2016084280A (ja) | 2016-05-19 |
US20100084016A1 (en) | 2010-04-08 |
CN105271723A (zh) | 2016-01-27 |
CA2739098A1 (en) | 2010-04-15 |
US10196297B2 (en) | 2019-02-05 |
KR101891459B1 (ko) | 2018-08-23 |
JP6042613B2 (ja) | 2016-12-14 |
KR20110066225A (ko) | 2011-06-16 |
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