CN102971264A - 利用溢流下拉熔合法通过共拉制制备的多层玻璃片 - Google Patents

利用溢流下拉熔合法通过共拉制制备的多层玻璃片 Download PDF

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CN102971264A
CN102971264A CN2011800326000A CN201180032600A CN102971264A CN 102971264 A CN102971264 A CN 102971264A CN 2011800326000 A CN2011800326000 A CN 2011800326000A CN 201180032600 A CN201180032600 A CN 201180032600A CN 102971264 A CN102971264 A CN 102971264A
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D·C·布克宾德
K·L·豪斯
P·坦登
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Abstract

具有增大的机械强度的透明玻璃片,其包括被表面压缩层包围的内层,其中内层与表面压缩层之间的热膨胀系数的差异大于50×10-7-1,表面压缩层的压缩应力至少约为300兆帕。

Description

利用溢流下拉熔合法通过共拉制制备的多层玻璃片
相关申请交叉参考
本申请要求2010年6月29日提交的题为“具有改善的机械强度的玻璃片(Glass Sheets with Improved Mechanical Strength)”的美国临时专利申请第61/359409号的权益和优先权,其内容作为本申请的基础并通过参考全文结合于此。
发明领域
本发明一般涉及玻璃片,更具体涉及具有改善的机械强度的玻璃片。
背景技术
人们长期认为,若玻璃的外表面处于压缩状态,则玻璃制品的机械强度能显著增大。人们也已经研究了通过使用热膨胀系数(CTE)存在差异的相邻玻璃层来强化玻璃。
另外,已知通过采用离子交换法能显著增加玻璃片的机械强度。但是,这些方法会受到离子交换量的限制,能实现的离子交换量取决于玻璃的组成和尺寸。另外,这些方法显著增加了生产成本和时间,需要大量额外的生产场地,并存在废物处理问题。因此,期望提供具有增大的机械强度的玻璃片,同时在玻璃的生产或处理中不需要离子交换过程。
发明概述
本发明的一种实施方式涉及一种透明玻璃片,其包括表面压缩层和与所述表面压缩层相邻的内层。在0-300℃,内层和表面压缩层之间的热膨胀系数差异大于50×10-7-1,表面压缩层的压缩应力至少约为300兆帕。
另外的特性和优点在以下详细说明中提出,部分特性和优点对于阅读了本说明书的本领域技术人员而言是显而易见的,或者可通过如本说明书及其权利要求以及附图所述实现实施方式而了解。
应该理解,以上一般说明和以下详细说明都只是示例性的,意在提供理解权利要求的性质和特性的概况或框架。
附图提供进一步的理解,附图结合在本说明书中并构成说明书的一部分。附图图示说明了一种或多种实施方式,与说明部分一起用于解释各种实施方式的原理和操作。
附图简要描述
图1示出本文揭示的玻璃片的截面图;和
图2示出可用于制造单层熔合拉制玻璃片的熔合拉制设备的透视图;和
图3示出熔合拉制设备的一部分的截面端视图,该设备具有上方成形容器和下方成形容器,可用于实现本文揭示的实施方式。
发明详述
我们提出一种制造表面上具有压缩应力的透明玻璃片的方法,其中,对于宽范围的组成、尺寸和厚度,可容易地调节玻璃片中压缩应力的量和压缩层的厚度。
如本文所用,术语“透明”用于表示这样一种固体材料,即穿透该材料的可见光谱中至少80%的辐射能传输通过该材料,而不是被该材料吸收或散射。特别优选的透明材料包括这样一些材料,即穿透该材料的可见光谱中至少95%的辐射能传输通过该材料,而不是被该材料吸收或散射。
如本文所用,术语“原位结晶过程”表示这样一种过程,即对可结晶成形的玻璃施加热处理方案,其中以预定速率将玻璃温度从等于或低于其退火点的温度升高到高于其退火点的温度,在高于其退火点的第一温度保持预定时间,然后以预定速率降低到低于其退火点的温度,使得进行该热处理方案之后处于结晶状态的玻璃百分比显著提高。
如本文所用,术语“离子交换法”表示这样一种方法,在该方法中,将成形的已加热玻璃浸入所含离子的半径大于玻璃表面中存在的离子半径的已加热溶液中,其中较小的离子被较大的离子置换,玻璃的机械强度得以增大。
如本文所用,术语“基本不含BaO”表示玻璃包含小于约0.1摩尔%的BaO。
如本文揭示的在表面上具有压缩应力的透明玻璃片包括这样一种透明玻璃片,其包括表面压缩层和与所述表面压缩层相邻的内层。这种玻璃片可采用熔合拉制法制造,其中将表面压缩层拉到内层的外侧。图1显示了玻璃片10的截面图,玻璃片10包括包围内层14的表面压缩层12,其中玻璃片截面的中心用x=0表示,玻璃片截面的最外边缘用x表示。
熔合拉制法使用一种拉制槽,其具有通道,用于接受熔融的玻璃原料。该通道有堰,堰在顶部沿着通道长度在通道两侧开放。当通道中注有熔融材料时,熔融玻璃从堰溢流。由于重力的原因,熔融玻璃沿拉制槽的外表面流下。这些外表面向下并向内延伸,直至在拉制槽下方的边缘处结合。两个流动的玻璃表面在该边缘处结合并熔合形成单独的流动片。熔合拉制法的优点在于,由于流过通道的两块玻璃膜熔合在一起,所以制得的玻璃片的任何一个外表面都不会与设备的任何部分接触。因此,表面性质不会受到所述接触的影响。
图2显示了可用于制造单层熔合拉制玻璃片的熔合拉制设备的透视图。熔合拉制设备包括成形容器135,其包括开口136,用于接收熔融玻璃126,所述熔融玻璃流进凹槽137中,然后溢流并沿两个侧面138a和138b流下,然后在称为根部139的位置熔合在一起。根部139是两个侧面138a和138b汇合在一起以及熔融玻璃126的两个溢流壁再结合(例如再熔合)在一起的位置,然后通过牵拉辊组件140a将熔融玻璃向下拉制,以形成玻璃片105。牵拉辊组件140a包括第一辊组件200和第二辊组件202。第一辊组件200包括支撑着第一辊206的两个牵拉辊支撑臂204a和204b。类似地,第二辊组件202包括支撑着第二辊212的两个牵拉辊支撑臂210a和210b。牵拉辊组件104a还包括差动驱动器214(例如装置155),其包括相连的马达216(例如1马力马达216),用于驱动差动轴218,进而驱动两个90°齿轮箱220和222。第一90°齿轮箱220相接并驱动第一辊206。并且第二90°齿轮箱222相接并驱动第二辊212。
可通过改进图2中所示的熔合拉制设备来制造本文揭示的玻璃片,提供的透明玻璃片具有被表面压缩层包围的内层。具体来说,图2中所示的熔合拉制设备可进行改进,从而具有分配表面压缩层的容器和分配将要被表面压缩层包围的内层的容器。图3中显示了这种熔合拉制设备的一部分的截面端视图。熔合拉制设备包括上方成形容器131′和下方成形容器135′。上方成形容器131′包括开口(未显示)以接收用于表面压缩层的熔融玻璃128′,下方成形容器135′包括开口(未显示)以接收用于内层的熔融玻璃126′。熔融玻璃126′流进凹槽137′中,从两个侧面138a′和138b′溢流,然后在根部139′熔合在一起。熔融玻璃128′流进凹槽133′中,然后在熔融玻璃126′上溢流,形成玻璃片105′。若需要额外的玻璃层,则可改进熔合拉制设备以包括额外的容器,用于分配额外的层。在其他方面中,熔合拉制设备可类似于图2中所示,包括牵拉辊组件140a。
如本文所述拉制透明玻璃片时,若表面压缩层和内层的热性质和机械性质不同,则在拉制过程中会引发应力。具体来说,由于不同层之间的热性质和粘度的不匹配,在拉制过程中会引发热应力和机械应力。若内层的热膨胀系数(CTE)大于表面压缩层的CTE,或者若内层的粘度大于表面压缩层的粘度,则可在表面压缩层中获得压缩应力。
当表面压缩层和内层的CTE和粘度都不匹配时,可通过热(CTE不匹配)应力和机械(粘度不匹配)应力的叠加计算总应力,即:
σzz,热z,机械  (1)
对于双层玻璃片,可按下式计算给定位置的热应力:
其中T是设定温度,T是室温,E是杨氏模量,α是热膨胀系数,ν是泊松比。
参数c(T)是面积平均的CTE,按下式计算:
Figure BDA00002679830000042
玻璃片的不同层中的不同玻璃也会导致具有不同的粘度和杨氏模量的不同区域。按下式估算粘度/杨氏模量不匹配应力:
其中F是拉制过程中的拉制牵引力,A是玻璃片的截面面积(A=2x W),η和E是位置x处的粘度和杨氏模量。
本文揭示的透明玻璃片具有表面压缩层,其中该表面压缩层的压缩应力至少约为300兆帕。称该表面压缩层的压缩应力至少为300兆帕,是指该表面压缩层处于压缩状态中,该压缩应力的量级或绝对值至少为300兆帕。压缩应力值可使用偏光计通过光弹性测量确定,如ASTM F218“玻璃中应力的标准分析方法(StandardMethod for Analyzing Stress in Glass)”中所述,其全部内容通过参考结合于此。
本文中所指的热膨胀系数(CTE)是给定材料或层在0-300℃之间的平均CTE。
玻璃层或区域的软化点定义为该温度或区域中的玻璃粘度等于约107.6泊(即3.981×107)时的温度。可采用ASTM C338-93(2008)“玻璃软化点的标准测试方法(Standard Test Method for Softing Point of Glass)”测定玻璃软化点和玻璃在软化点附近温度时的粘度,其全部内容通过参考结合于此。
本文揭示的玻璃片的内层和表面压缩层的CTE差大于50×10-7-1,例如大于75×10-7-1,例如大于90×10-7-1,包括50×10-7-1至100×10-7-1之间,还包括75×10-7-1至100×10-7-1之间,其中内层的CTE大于表面压缩层的CTE。内层与表面压缩层的CTE比优选大于2.5,例如大于3,又如大于3.5,再如大于4,包括2.5-5,例如3-5。在一组示例性的优选实施方式中,表面压缩层的CTE范围是约25×10-7-1至约35×10-7-1,内层的CTE范围是约75×10-7-1至约125×10-7-1
虽然本文揭示的实施方式包括其中表面压缩层和内层的软化点等于或接近于同一温度的情况,或者表面压缩层的软化点高于内层的软化点的情况,但是,在一些优选的实施方式中,表面压缩层的软化点比内层的软化点至少低40℃,例如比内层的软化点至少低60℃,又如比内层的软化点至少低80℃,再如比内层的软化点至少低100℃,还如比内层的软化点至少低120℃。例如,在一些优选的实施方式中,表面压缩层的软化点与内层的软化点之间的差异为40-150℃,例如为60-150℃,又如为80-150℃,再如为100-150℃。在内层软化点±200℃的范围内,表面压缩层的粘度与内层的粘度的比值优选约为0.1-0.9,例如约为0.1-0.5,又如约为0.1-0.3,再如约为0.1-0.2。
本文揭示的一个或多个内层的厚度与玻璃片的总厚度之间的比值优选至少约为0.8,例如至少约为0.85,又如至少约为0.9,再如至少约为0.95。虽然不限于任何具体厚度,但是本文揭示的玻璃片的厚度优选约为0.3-3毫米,例如约为0.3-1.5毫米。
本文揭示的透明玻璃片的拉制牵引力优选至少约为5磅,例如至少约为25磅,又如至少约为50磅,再如至少约为100磅,包括约5-250磅,例如约25-200磅。
表面压缩层和内层的CTE和粘度性质以及它们的相对厚度和拉制玻璃片的力应当进行选择,使得表面压缩层的压缩应力至少约为300兆帕,例如至少约为400兆帕,又如至少约为500兆帕,再如至少约为600兆帕,还如至少约为700兆帕,包括约300-1000兆帕,例如约500-1000兆帕。
在一组示例性的优选实施方式中,表面压缩层包含碱土金属硼铝硅酸盐玻璃,内层包含碱金属铝硅酸盐玻璃。用于表面压缩层中的碱土金属硼铝硅酸盐玻璃的CTE约为25×10-7-1至约35×10-7-1。用于内层中的碱金属铝硅酸盐玻璃的CTE优选约为75×10-7-1至约125×10-7-1
以氧化物为基准按重量百分比计,用于表面压缩层的碱土金属硼铝硅酸盐玻璃优选包含:(i)65≤SiO2≤75%;(ii)7≤Al2O3≤13%;(iii)5≤B2O3≤15%;(iv)5≤CaO≤15%;(v)0≤BaO≤5%;(vi)0≤MgO≤3%;和(vii)0≤SrO≤5%。优选碱土金属硼铝硅酸盐玻璃基本不含BaO。可用于表面压缩层中的碱土金属硼铝硅酸盐玻璃的一个例子是
Figure BDA00002679830000061
玻璃,从康宁公司(Corning Incorporated)得到。
以氧化物为基准按重量百分比计,用于内层的碱金属铝硅酸盐玻璃优选包含:(i)50≤SiO2≤65%;(ii)10≤Al2O3≤20%;(iii)0≤MgO≤5%;(iv)10≤Na2O≤20%;(v)0≤K2O≤5%;和(vi)≥0且≤1%的B2O3、CaO、ZrO2和Fe2O3中的至少一种。可用于内层的碱金属铝硅酸盐玻璃的一个例子是玻璃,从康宁公司得到。
表面压缩层和内层可各自任选地包含另外的材料或掺杂剂,从而进一步改进它们的CTE和/或粘度性质。
在本文所述的透明玻璃片的优选实施方式中,透明玻璃片的任何层都没有经历原位结晶过程。优选玻璃片的任何层中小于10ppm处于结晶状态中,更优选玻璃片的任何层中小于5ppm处于结晶状态中,更优选玻璃片的任何层中小于1ppm处于结晶状态中。
优选透明玻璃片的任何层都没有经历离子交换过程。
为了检测CTE(热应力)、厚度比和粘度(机械应力)对压缩应力的影响,以一系列示例性的玻璃片为模型,它们具有变化的表面压缩层与内层之间的CTE比和粘度比,以及变化的内层厚度与玻璃片总厚度之间的比值。以下表中报告的各玻璃片为模型,它们的厚度为0.05厘米,宽度为35厘米,以50磅的牵引力进行拉制。以各例子中的玻璃片的表面压缩层为模型,它们的CTE约为31.8×10-7-1,软化点约为985℃。对于表中报告的各例子,内层与表面压缩层的粘度比以这些层在表面压缩层软化点附近温度的对应粘度为基础,所述温度具体是约985℃,在该温度下,各例子中表面压缩层的粘度约为3.981×107泊。
表1中列出了示例性的模型玻璃片,其中在各例子中,内层与表面压缩层的CTE比约为3(即,内层的CTE约为95.4×10-7-1,使得内层与表面压缩层之间的CTE差约为63.6×10-7-1)。
表1
表2中列出了示例性的模型玻璃片,其中在各例子中,内层与表面压缩层的CTE比约为4(即,内层的CTE约为127.2×10-7-1,使得内层与表面压缩层之间的CTE差约为95.4×10-7-1)。
表2
Figure BDA00002679830000072
Figure BDA00002679830000081
通过形成压缩应力至少为300兆帕的表面压缩层,本文揭示的透明玻璃片可具有改善的机械性质,尤其是不需要经历离子交换过程就能获得增大的机械强度。
除非另外指明,否则,不应以任何方式将本文提出的任何方法理解为要求按特定顺序进行各步骤。因此,当一种方法权利要求未实际描述进行各步骤所遵循的顺序时,或者未在权利要求或描述部分中具体指出各步骤限于特定顺序时,不应以任何方式推断任何具体顺序。
对本领域技术人员显而易见的是,可以在不偏离本发明精神或范围的情况下进行各种修改和变化。由于本领域技术人员可结合本发明的精神和内容对所揭示的实施方式进行修改组合、子项组合和变化,所以本发明包括所附权利要求及其等同项的范围内所有内容。

Claims (19)

1.一种透明玻璃片,其包括表面压缩层和与表面压缩层相邻的内层,其中内层和表面压缩层在0-300℃的热膨胀系数的差异大于50×10-7-1,表面压缩层的压缩应力至少约为300兆帕。
2.如权利要求1所述的透明玻璃片,其特征在于,内层与表面压缩层在0-300℃的热膨胀系数的比值大于2.5。
3.如权利要求1所述的透明玻璃片,其特征在于,所述透明玻璃片具有一定厚度,所述内层具有一定厚度,内层厚度与透明玻璃片厚度的比值至少约为0.8。
4.如权利要求1所述的透明玻璃片,其特征在于,所述透明玻璃片的厚度在约0.3-3毫米范围内。
5.如权利要求1所述的透明玻璃片,其特征在于,所述表面压缩层的软化点比内层的软化点至少低40℃。
6.如权利要求1所述的透明玻璃片,其特征在于,在内层软化点±200℃的范围内,所述表面压缩层与内层的粘度比约为0.1-0.9。
7.如权利要求1所述的透明玻璃片,其特征在于,以氧化物为基准按重量百分比计,所述内层包含:(i)50≤SiO2≤65%;(ii)10≤Al2O3≤20%;(iii)0≤MgO≤5%;(iv)10≤Na2O≤20%;(v)0≤K2O≤5%;和(vi)≥0且≤1%的B2O3、CaO、ZrO2和Fe2O3中的至少一种。
8.如权利要求1所述的透明玻璃片,其特征在于,以氧化物为基准按重量百分比计,所述表面压缩层包含:(i)65≤SiO2≤75%;(ii)7≤Al2O3≤13%;(iii)5≤B2O5≤15%;(iv)5≤CaO≤15%;(v)0≤BaO≤5%;(vi)0≤MgO≤3%;和(vii)0≤SrO≤5%。
9.如权利要求8所述的透明玻璃片,其特征在于,所述表面压缩层基本不含BaO。
10.如权利要求1所述的透明玻璃片,其特征在于,所述表面压缩层的压缩应力至少约为500兆帕。
11.如权利要求1所述的透明玻璃片,其特征在于,所述透明玻璃片的任何层都没有经历原位结晶过程。
12.如权利要求1所述的透明玻璃片,其特征在于,所述玻璃片的任何层中小于10ppm处于结晶状态中。
13.如权利要求1所述的透明玻璃片,其特征在于,所述透明玻璃片的任何层都没有经历离子交换过程。
14.如权利要求1所述的透明玻璃片,其特征在于,内层与表面压缩层在0-300℃的热膨胀系数的比值大于3。
15.如权利要求1所述的透明玻璃片,其特征在于,内层与表面压缩层在0-300℃的热膨胀系数的差异大于75×10-7-1
16.如权利要求1所述的透明玻璃片,其特征在于,透明玻璃片具有一定厚度,内层具有总厚度,内层总厚度与透明玻璃片厚度之间的比值至少约为0.9。
17.如权利要求1所述的透明玻璃片,其特征在于,内层与表面压缩层在0-300℃的热膨胀系数的比值大于4。
18.如权利要求1所述的透明玻璃片,其特征在于,内层与表面压缩层在0-300℃的热膨胀系数的差异大于90×10-7-1
19.如权利要求1所述的透明玻璃片,其特征在于,所述表面压缩层的压缩应力至少约为700兆帕。
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