CN101980985A - 覆盖有薄层的玻璃 - Google Patents

覆盖有薄层的玻璃 Download PDF

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CN101980985A
CN101980985A CN2009801100108A CN200980110010A CN101980985A CN 101980985 A CN101980985 A CN 101980985A CN 2009801100108 A CN2009801100108 A CN 2009801100108A CN 200980110010 A CN200980110010 A CN 200980110010A CN 101980985 A CN101980985 A CN 101980985A
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layer
glass
oxide
upper layer
nicr
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G·迪斯特法诺
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AGC Glass Europe SA
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  • Surface Treatment Of Glass (AREA)
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Abstract

本发明涉及基本上透明的玻璃，其包含在真空下利用磁控管沉积的薄层体系并具有防阳光和/或低辐射的性能，包含作为保护性表面层的基于钛氧化物和至少一种具有高硬度的其它金属氧化物的层，所述具有高硬度的其它金属氧化物选自包含ZrO2、SiO2、Cr2O3的组。根据本发明的玻璃具有这样的性质：耐受550℃的热处理5分钟而不引起光学缺陷(尤其是呈色和虹彩)的存在。这些玻璃是可钢化的。

Description

覆盖有薄层的玻璃
技术领域
本发明涉及包含一组薄层的玻璃(vitrages)，所述薄层赋予防阳光或低辐射性能，并能够经得起弯曲/钢化类型的热处理。
背景技术
最常用于所讨论的玻璃的涂层是在真空下通过磁控管辅助的沉积技术(所谓“磁控溅射”)来实现的。
通过这种方式沉积的层体系使得能够不论在热特性方面还是在光学方面都达到卓越的性能。它们可以尤其具有非常大的选择性，换言之构成了对于红外线的强大滤波器，同时允许可见波长通过。在最佳的情况下，它们可以提供理想的反射中性，从而尤其避免了不希望的呈色。
除了所寻求的性质以外，所讨论的玻璃还应当具有对于它们可能遭受的各种各样侵害的足够耐受性(résistance)。这尤其涉及化学侵害：空气、水、盐雾...，但也涉及在其使用当中，在运输或转化过程中它们经受的机械侵害。
玻璃还经历诸如钢化(trempe)或弯曲这样的变态，这意味着在550-700℃的温度下的热处理。这些玻璃的层体系应当对这些处理不太敏感或不敏感，换言之，它们的特征应当保持基本不变。尤其是，玻璃应当保持没有如下这样的缺陷，该缺陷改变光学特性，尤其是透明度，或者由于例如斑点或虹彩的形成而改变其外观。
具有这些防阳光和/或低辐射性能的玻璃体系地包含一组反射红外线的所谓功能层，以及一组保护前面的层并且最小化可见波长反射的介电层。
在保护层中，最外面的那些层尤其应当赋予这些体系前面已讨论的机械和化学耐受性能，当然同时不改变其它性能。然而，指示性地，以其机械耐受性(résistance mécanique)著称的层，尤其是某些碳化物，例如钛或锆的碳化物，是过于吸收性的，以致于不能被使用，即使是在非常薄的厚度下。
以前的各种提议至少部分地满足了与这些也被称作“顶涂层(top-coat)”的表面层有关的要求。在最常用的层当中，尤其列举钛氧化物层、锡氧化物层、二氧化硅层、氮化物或氧氮化物尤其是硅和/或Al的氮化物或氧氮化物的层。根据经验，钛氧化物或锡氧化物层对热处理过于敏感。氮化钛、氧氮化锆尤其显示出良好的耐热处理性，因为它们在热处理之后提供了所需的特性。然而，这些层在处理之前和之后具有明显的光透射变化，这使得不可能将未经处理的玻璃置于其它经处理的玻璃旁边。
已提出了允许将热处理之前和之后的玻璃相组合的表面层。这尤其涉及二氧化硅和氮化硅。二氧化硅的沉积非常困难，而氮化硅层只具有不足的耐刮划性。
发明内容
本发明提出用于这些防阳光和/或低辐射体系的表面层，其提供一组相对于现有体系的性能而言经改善的性能。
本发明提出作为表面层布置基于钛氧化物和至少一种具有高硬度的其它金属氧化物的层，所述具有高硬度的其它金属氧化物选自包含ZrO2、SiO2、Cr2O3的组。
钛氧化物和其它金属氧化物的各自比例可以涵盖大的范围。为了使效果明显，该一种或多种附加的氧化物应当占整体(ensemble)的至少5％重量，优选至少10％重量。
在混合氧化物中，钛氧化物以至少40％重量存在，优选地以至少50％重量存在。
特别优选地，钛氧化物占至少55％重量。
在根据本发明使用的混合氧化物中，除了钛氧化物以外，锆氧化物由于其非常高的硬度是特别优选的。它有利地以表面层的15至50％重量的比率存在。
除了钛氧化物和上面列举的金属氧化物以外，根据本发明的表面层还可以包含前述氧化物的几乎不可分离的额外氧化物。镧系元素如钇的氧化物或铪的氧化物尤其是这种情况。当存在这些额外氧化物时，它们的含量保持相对有限并且不超过整体的8％重量，通常保持小于5％。
为了合适地发挥其保护作用，表面层应当具有一定的厚度。然而，如果安排该层仅为了其赋予层体系的机械性能，那么相对适度的厚度就足够了。优选地，这个层的厚度不小于3nm。
考虑到在这个表面层的组成中所含的氧化物是很透明的，那么可能的是，使用比改善耐受性需要的厚得多的层。尤其可使用此保护层作为干涉滤波器的成分，换言之，作为显著地参与维持高的可见透射和参与建立良好反射中性的层。
用作干涉滤波器成分的表面层有利地与其它的介电层组合。因此，整体的选择不仅考虑不同层的光学或结构性能(指数、透明度、晶体结构、界面性质)，而且也要考虑形成这些层的相对方便性。
无论所考虑的结构如何，实际上，根据本发明的表面层保持至多等于35nm的厚度。
在需要时，根据本发明的层体系还可包含多个保护性表面层。基于钛氧化物的层可以与其它旨在进一步改善耐热处理性的层相结合。位于基于钛氧化物的层之下的这种类型的层尤其是金属钛的层，其在这种热处理过程中发生氧化。还可以涉及氮化钛、氧氮化钛的层，或者TiZr的氮化物或TiZr、Zr的氮化物或Zr、钛和铌的氧化物的层。
尤其赋予非常好机械性能的根据本发明的表面层还可以有利地与提供大的化学试剂耐受性的层组合。这种类型的层尤其是氮化硅和氧氮化硅的层(任选地具有在阴极中作为掺杂剂存在的铝)。这些层紧接地位于保护性表面层并且尤其是基于钛氧化物的层的下面。这些额外的层具有也可以是大约几纳米的相对适度的厚度。
根据本发明的表面层对弯曲或钢化的热处理不太敏感或不敏感。在至少550℃的温度下经历5分钟且对于20nm的厚度来说，其光透射变化不多于0.1％。指示性地，覆盖有TiN机械耐受性层的类似玻璃在相同的条件下显示出大的翘曲。
根据本发明的经覆盖的玻璃有利地具有根据形成标准ASTM 2486D的主题的方法的耐刮划性，在0至100％的范围内，其不大于30％，优选地不大于20％，100％对应于完全刮划的玻璃。
根据本发明的经覆盖的玻璃还提供对湿度测试的非常好的耐受性。经受根据标准ISO 6270的“Cleveland”测试并且在3天的期间，所达到的水平有利地为1至5等级中的至少3，5对应于完全设有缺陷的玻璃。对于经受根据标准EN 1096的盐雾化测试的样品，结果有利地是在2天暴露后大于3。
根据本发明的包含“顶涂层”的体系尤其符合下述结构：
玻璃/阻挡(blocage)层/核化层/Ag/隔离(barriere)/介电/顶涂层。
玻璃/阻挡层/核化层/Ag/隔离/介电/核化层/Ag/隔离/介电/顶涂层。
玻璃/阻挡层/核化层/Ag/隔离/介电/核化层/Ag/隔离/介电核化层/Ag/隔离/介电//顶涂层。
附图说明
在也作为附图主题的下述实施例中详细地描述本发明，其中：
-图1是覆盖有对比层体系的玻璃的剖面示意图；
-图2表示根据本发明的类似层体系；
-图3是表示对于根据本发明使用的氧化物单层而言根据波长而变化的光吸收的图；
-图4在更详细的比例尺下与前一个图类似。
具体实施方式
出于清楚的考虑，图1中的玻璃以剖面形式呈现而没有遵守不同成分的比例。玻璃片材1覆盖有一组包含基于反射红外线的银的层4的层。此银层被布置在两组介电层之间，所述介电层对其进行保护并赋予其具有良好反射中性的良好光透射。
银层4有利地沉积在基于锌氧化物的层3上。锌氧化物的层以及基于掺杂的锌氧化物的层已知有助于与银层的良好界面的形成，而不粗糙。它们整体上改善了后者的性能。对于相同量的每单位面积的银，所述层的传导以及因此的辐射率在它们以这种方式沉积时得到了改善。可以只涉及小厚度的锌氧化物，该厚度不大于15nm。
当锌氧化物的厚度较大时，风险是产生柱状生长，其导致具有增加的粗糙度的不太规则的界面。为了避免这种类型的生长，已知的是以其它氧化物尤其是锡、铝或镓的氧化物掺杂锌氧化物。
由锌和锡混合氧化物构成的层传统上是两种类型的。在其上沉积银层的层有利地具有低的锡氧化物含量，尤其是大约10％重量。如前所示，这些层相对不太厚并且不超过15nm。第二种类型的锌和锡的混合氧化物层用于在介电组中构成去反射效果的光路的主要部分。在该功能中，所讨论的该一个或多个层通常具有几十纳米的厚度。典型地，这种类型的层由混合氧化物构成，该混合氧化物具有锌和锡的氧化物各大约50％重量。这些层具有大稳定性的优点，尤其是在玻璃可能经受的热处理中。
在图1所表示的实施例中，保护性层5沉积在银层4之上。这涉及传统层，其目的在于保护银层对抗特别是在后来的沉积当中可能影响银层的改变，尤其是当这些沉积是例如在氧化性气氛中根据反应性模式来实现时。层5在介入与气氛的反应时是所谓的“阻挡”或者“牺牲”层，所述气氛在没有这个层存在时可与铝层反应。
这些牺牲层具有非常小的厚度。它们不大于6nm，并且优选地，其厚度为2或3nm。它们通常基于氧化物而构成，尤其是钛氧化物，或者NiCr的混合氧化物、锆氧化物，钛氧化物提供非常大透明度的优点。由于是为了能够在保护银时发生反应而沉积，因此它们通常从相应的金属开始来形成，并在之后的堆积构成中进行氧化。由于此原因，这些层经常是亚化学计量的。还可能的是，从本身是亚化学计量的陶瓷靶开始沉积。这种实施方式使得能够在最终层中更方便地达到接近化学计量的良好的氧化。以此方式，所述层的消光系数被最佳地降低。
在图1中，层2、6和8是属于滤波器构造中的层。它们使得能够避免大部分可见范围光线的反射。借助于这些层，还可以调节透射的光并且尤其是反射的光的呈色，已知在大多数的应用中，对于后者力求做到这种光尽可能地弱和中性。
传统的介电层主要由Zn、Sn、Ti、Al、Zr、Nb的氧化物构成。它们的厚度取决于它们的指数和所需的光路，而光路本身取决于反射红外线的层的厚度。这些量值之间的关系已完全建立并且通常借助于专门的程序进行确定。以如此确定的值为起始进行之后的调节以考虑在结构、组成或构造的有效特性和理想层的相应特性之间可能存在的偏差。
表面层7是对抗机械侵害的保护性表面层。
根据本发明(图2)，层7基于包含高硬度的氧化物(ZrO2，SiO2，CréO3)的钛氧化物。
在图1中显示了对比实施例。在这个实施例中，表面层由氮化钛，或由覆盖有石墨层的氮化钛层构成。
针对可钢化(trempable)的产品，也即针对其光学性能和光能量性能(光透射、辐射、呈色...)在高温下耐受热处理的产品，进行了一系列测试。
将根据本发明的产品的性质与其表面层不符合本发明条件的类似产品的性质进行对比。
实现下面的结构：
  ZSO5   ZSO9   Ag   TiOx   ZSO9   ZSO5   TiN   C
 对比实施例1   250   100   95   50   100   250   35
 对比实施例2   250   100   95   50   100   250   35   30
  层   2   3   4   5   6   8   7   7
  ZSO5   TiZrOx   ZnO-Al   Ag   TiOx   ZSO9   ZSO5   TiZrOx
 实施例1   180   100   80   120   50   80   235   100
 实施例2   180   100   80   120   50   80   235   50
  层   2   9   3   4   5   6   8   7
在这些表中，缩写的含义是：
-ZSO5是每种成分为50％重量的锌和锡的混合氧化物；
-ZSO9意指掺杂有10％重量的锡氧化物的锌氧化物层；
-TiOx是低氧化的钛氧化物；
-TiZrOx是混合的钛氧化物，包含以重量计50％的TiO2、46％的ZrO2，其余由通常伴随锆的成分尤其是氧化物Y2O5构成；这种氧化物可以是化学计量的或亚化学计量的；
-ZnO-Al是掺杂具有5％铝含量的铝的锌氧化物；
-TiN是氮化钛；
-C是通过在惰性气氛下从石墨阴极开始形成而获得的石墨层。
根据本发明的结构与现有产品的例子的区别在于表面层的性质。氮化钛层是传统的。石墨涂层通过一种“润滑作用”避免与下面的层接触而增添了机械耐受性。根据本发明，这些层由包含占大比例的锆氧化物的钛氧化物代替。
根据标准ASTM 2486D进行的耐刮划性测试导致如下结果。
对比实施例1和2的刮划比率分别是40％和10％。对于该实施例2，碳层的存在明显改善了结果，但是使生产复杂化。而且，它在玻璃经受的热处理过程中必须应当是“燃烧的”，以便不改变光透射。
对于实施例1和2，根据本发明的结构分别具有10％和5％的刮划比率。换言之，所述产品与现有的最好产品至少是一样耐受的，另外还提供了良好的光透射。
用基于钛和硅的混合氧化物(TiOx-Si)的表面层进行其它测试。硅氧化物是8％重量。这些层的沉积在中性气体(Ar)或在包含7％氧气的中性气体和氧气的混合物中进行。针对该表面层还在不同的厚度(30，80和
Figure BPA00001275673200071
)测试了这些结构。
层体系的结构与之前的实施例1的结构类似。
  TiO2   ZSO9   Ag   TiOx   ZSO9   TiOx-Si
  180   60   120   20   210
TiO2在导致几乎是化学计量的氧化物的条件下进行沉积。
进行下面的组合并且所指示的性能是耐干刷子刮划性以及耐“Cleveland”型化学测试的性能。
所有“Cleveland”测试显示出非常好的耐受性。评分在1至5的等级中都位于4或更高。耐刷子的性能显示出以刮划百分比表示的如下结果：
Figure BPA00001275673200072
对于在包含氧的气氛下沉积的层而言，耐磨性显示出明显的进步。这种改善在具有硅的混合氧化物的情况下特别明显。这种耐刮划性也在较少的程度上取决于层的厚度。一般地，具有铝的混合氧化物更具机械耐受性。
碳层因其耐磨性而被用作层体系的保护是已知的。这些碳层的使用尤其旨在贮存和运输的生产过程中的保护。这些层的存在，即使是小厚度的，通常都会造成光透射的改变。这些层的厚度一般不超过15nm并且优选地不超过10nm。出于这个原因，这些层通常是被临时使用的。它们会被去除以重建下面的层体系。可以使用各种方法来去除碳层。为了实现完全的除去，最有效的技术对应于通过在升高温度下的氧化进行去除。因此，为能耐受高温而设计的本发明层体系特别适合于借助碳层的额外保护。
制备再现对比实施例1和2的结构的样品，除了它们的层7之外。在对比实施例中，这个层是TiN和覆盖有碳的TiN。在根据本发明的实施例中，层7由钛-锆混合氧化物以及覆盖有碳的此相同层构成。所述结构为(厚度总是用
Figure BPA00001275673200081
表示)：
  ZSO5   ZSO9   Ag   TiOx   ZSO9   ZSO5   TiN或TiZrOx   C
  对比实施例1   250   100   95   50   100   250   35
  对比实施例2   250   100   95   50   100   250   35   30
  实施例3   250   100   95   50   100   250   35
  实施例4   250   100   95   50   100   250   35   30
  层   2   3   4   5   6   8   7   7
前面已报告了对于对比实施例的耐刮划性的测试(40和10％)。对于根据本发明的两个样品，所观察到的刮划比率分别是约10和5％。在两个系列中因而很好地观察到了由于碳层的存在所带来的改善。同样，在相同的结构下，基于钛和锆的混合氧化物的表面层的存在更具耐受性。
使前述样品经受一系列耐受性测试。
第一个测试是根据作为标准ISO 6270的主题的所谓“Cleveland”方法的抗冷凝性。根据这种测试，样品在恒定温度下在饱和湿度的气氛中保持数天。注意可能出现的缺陷和它们的密度。当1天后达到的水平是1至5的等级中的4时，该测试被认为是成功的，5对应于没有缺陷的样品。
还在气候室中进行测试。其同样涉及抗冷凝性的测试。在这个测试中，温度交替地从45至55℃，每次1小时。气氛也是湿度饱和的。如前那样，当3天后的水平是1至5等级中的至少3时，结果良好。
盐雾化测试根据标准EN1096来进行。在这种情况下，当2天后的水平是仍为1至5任意等级中的至少2.5时，样品是令人满意的。
通过加速暴露确定耐UV性。如果水平是至少3则是令人满意的。
将所获得的结果报告在下表中：
 Cleveland 3天  气候室3天   盐雾2天   UV
 对比实施例1   3.5   3.5   3.75   3.5
  实施例3   4   4   4.25   4
 对比实施例2   3.5   3.5   2.75   4
  实施例4   4.25   4.25   4   4
相对于参考样品，根据本发明的结构表现至少也很好，并且特别耐受湿度耐受性试验。
另一个系列的测试利用在基于钛氧化物的保护性层之下的钛或氮化钛层来进行。该层体系的结构如下(厚度用
Figure BPA00001275673200091
表示)：
玻璃/ZSO5(190)/TiZrOx(140)/ZSO9(50)/Ag(130)/Ti(50)/ZSO5(240)/顶涂层
保护性层“顶涂层”根据样品如下构成：
 对比实施例3   TiN   32
 对比实施例4   TiN   32   C
  实施例5   Ti   27   TiZrOx   30
  实施例6   Ti   30   TiZrOx   30
  实施例7   Ti   27   TiZrO   30
  实施例8   Ti   27   TiZrO   30
  实施例9   TiN   24   TiZrO   30
  实施例10   TiN   24   TiZrOx   30
注释与前述实施例中的一样。在这些注释中，Ti意指在中性气体气氛中从金属靶开始沉积的钛层。在这些条件下，所构成的层基本上是金属的。其在玻璃经受的随后热处理中将会被氧化。TiZrOx意指在也没有氧的气氛下从低氧化的陶瓷靶开始沉积的层。在这些条件下，所形成的层在热处理之前还依然是轻微低氧化的。TiZrO意指从相同类型的靶开始但在由具有8％氧气的氩气-氧气混合物组成的气氛中产生的层。在这些条件下，所形成的层几乎是化学计量的。
在670℃的温度下维持9分钟后，使样品经受钢化操作。两个对比样品出现令人不舒服的翘曲。根据本发明的样品5至10在这个热处理之后几乎没有明显的改变。
使同样的样品经受三个耐受性测试：对于盐雾(EN1096)、对于“湿法摩擦测试”(wet rub test)和对于刮划(ASTM2486D)。
“湿法摩擦测试”用于评价层体系在摩擦下的耐剥层性。在负荷下使样品经受保持湿润(脱盐水)的棉织物的摩擦。以60次振荡/分钟的频率进行往复摩擦。该运动保持通常为500的循环数。
观察表面层的变化以及该表面层是否由于这种摩擦而被除去。
对比样品3在两个试验中不足以耐机械磨损。对比样品4不满足盐雾试验。
根据本发明的样品5至10本身令人满意地满足这三个试验。
基于钛氧化物的根据本发明用作保护性表面层的层除了其机械耐受性以外还具有对可见光波长是非常透明的这样的优点。这种透明性因为层的氧化更完全而更好。图3和4示出了这种特殊性。
在这些图中，报告了随波长变化的一系列光吸收测量结果。所述测量在与前述实施例所提供的那些相同类型的钛和锆的混合氧化物的单层上进行。将所述层沉积在4mm厚度的透光玻璃片上。
TiZrOx层一致地是16nm。其在0.8Pa的恒定总压力下，在其中氧含量可变的氩气气氛下进行沉积。
从包含钛和锆的混合氧化物的陶瓷靶开始进行沉积。氧流量相继地为0(菱形)，接着1(圆形)、2.5(三角形)、5cm3(正方形)/Kw施加到阴极的功率。第五次测量(星形)对应于最后的样品(5cm3)，其已经受600℃的热处理3分钟。
在只有氩气的气氛中，层的光吸收(图3)是非常大的。这种吸收对应于在这种类型的气氛中的形成中的固有亚化学计量的存在。一旦引入少量氧，钛的反应能力就迅速导致根本不同的表现。光吸收明显减小。氧化物混合物趋向于化学计量。
在图3中，各种曲线非常接近。为了区别氧含量的效果，在图4中以另一比例尺报告结果。在该图中观察到，当氧含量增加时光吸收整体上更小。不过快速达到一个极限。经受热处理的样品所呈现的曲线与在这种处理前的样品的曲线几乎相同。对于这些浓度来说所述层因而是几乎化学计量的。
除了在前述实施例中给出的结构之外，以下尤其给出有利的结构，所述有利的结构包含根据本发明的表面层，也即硬氧化物和钛的混合氧化物的层，以及在其上布置有额外碳层的层，整体(ensemble)构成了保护性“顶涂层”层：
玻璃/TiO2/ZnO/Ag/NiCr/SiAlN/顶涂层
玻璃/ZSO5/TiO2/ZnO/Ag/隔离/SiAlON/顶涂层
玻璃/SiAlN/NiCr/Ag/NiCr/SiAlN/涂层
玻璃/SiAlN/ZnO/Ag/NiCr/SiAlN/顶涂层
玻璃/SiAlN/ZnO/Ag/NiCr/ZnO/SiAlN/ZnO/Ag/NiCr/顶涂层
玻璃/TiO2/ZnO/Ag/NiCr/SnO2/ZnO/Ag/NiCr/SnO2/顶涂层
玻璃/ZSO5/ZSO9/Ag/隔离/ZSO5/ZSO9/Ag/隔离/ZSO5/SiAlON/顶涂层。
在这些结构中，除了“顶涂层”之外，其它层在常规使用条件下使用并且用于发挥它们的传统功能：
-NiCr作为牺牲层；
-SiAlON作为指示和保护性层；
-TiO2和SnO2作为指示层；
-ZnO作为指示层，但当与银层接触和相对小厚度(小于10nm)时也有助于银层的生长。

Claims (19)

1.可钢化的基本上透明的玻璃，其包含在直空下利用磁控管沉积的薄层体系并具有防阳光和/或低辐射的性能，包含作为保护性表面层的基于钛氧化物和至少一种具有高硬度的其它金属氧化物的层，所述具有高硬度的其它金属氧化物选自包含ZrO2、SiO2、Cr2O3的组。
2.根据权利要求1的玻璃，其中该表面层的除了钛氧化物以外的一种或多种金属氧化物占所述层的整体的至少5％重量，并且优选至少10％重量。
3.根据前述权利要求之一的玻璃，其中钛氧化物占该表面层的至少40％重量。
4.根据前述权利要求之一的玻璃，其中所述表面层还包含通常与所考虑的附加氧化物一起存在的金属氧化物，这些氧化物以不超过该表面层的所有氧化物的8％重量的比例存在，优选小于5％重量。
5.根据前述权利要求之一的玻璃，其中除了钛氧化物以外，所述表面层包含比例为15至50％重量的锆氧化物。
6.根据前述权利要求之一的玻璃，其中该基于钛氧化物的表面层具有不小于3nm的厚度。
7.根据权利要求1至6之一的玻璃，其中该基于钛氧化物的表面层具有不大于35nm的厚度。
8.根据前述权利要求之一的玻璃，其中将该基于钛氧化物的保护性层施加于第一保护性层之上，所述第一保护性层由金属钛、或者氮化钛、Zr或者Zr的氮化物、TiZr或TiZr的氮化物构成。
9.根据前述权利要求之一的玻璃，其中所述表面层本身覆盖有碳层。
10.根据权利要求9的玻璃，其中所述碳层具有不大于30nm并且优选不大于20nm的厚度。
11.根据权利要求9或10的玻璃，其中所述碳层被临时应用，这个层通过在氧化性气氛下在热处理过程中的氧化而被去除。
12.根据前述权利要求之一的玻璃，其在根据标准ASTM 2486D进行的耐刮划性测试中导致至多等于30％并且优选至多等于20％的刮划比率。
13.根据前述权利要求之一的玻璃，其除了该表面层以外还包含至少一个基于银的功能层和一组介电层，所述介电层被布置在玻璃基材和第一银层之间，在需要时在每个银层之间，并且在离该基材最远的银层之上。
14.根据权利要求13的玻璃，其包含一个、两个或三个银层，每个的厚度为7至20nm。
15.根据前一个权利要求的玻璃，其中每个基于银的层覆盖有由NiCr、Nb、Zr、Ti的氧化物或低氧化物形成的牺牲层。
16.根据权利要求13或14的玻璃，其中该一个或多个银层沉积在基于任选地掺杂有锡或Al或Ga的锌氧化物的层上。
17.制备根据前述权利要求之一的玻璃的方法，其中所述基于钛氧化物的表面层包含一种或多种改善其机械耐受性的附加氧化物，该表面层从包含相应的氧化物或低氧化物的混合物的阴极开始，通过在真空下通过磁控管辅助的沉积技术进行沉积。
18.根据权利要求17的方法，其中所述表面层的沉积在轻微氧化性的气氛中进行。
19.根据权利要求1至7之一的玻璃，其中所述″顶涂层″表面层是下述组中的层体系的组成分，所述组包含：
玻璃/TiO2/ZnO/Ag/NiCr/SiAlN/顶涂层
玻璃/SiAlN/NiCr/Ag/NiCr/SiAlN/顶涂层
玻璃/SiAlN/ZnO/Ag/NiCr/SiAlN/顶涂层
玻璃/SiAlN/ZnO/Ag/NiCr/ZnO/SiAlN/ZnO/Ag/NiCr/顶涂层
玻璃/TiO2/ZnO/Ag/NiCr/SnO2/ZnO/Ag/NiCr/SnO2/顶涂层
下述层是以传统方式构成的，并且用于发挥其通常的作用，即：
-NiCr作为牺牲层；
-SiAlN作为指示和保护性层；
-TiO2和SnO2作为指示层；
-ZnO作为指示层，但当与银层接触和相对小厚度(小于15nm)时也有助于银层的生长。
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CN105814149B (zh) * 2013-12-12 2019-11-22 乐金华奥斯有限公司 低辐射涂敷膜、其的制备方法及包含其的窗户用功能性建材
CN105271823A (zh) * 2015-10-24 2016-01-27 揭阳市宏光镀膜玻璃有限公司 可钢化的高耐磨性金色双银low-e玻璃及其制备方法
CN106746731A (zh) * 2017-01-19 2017-05-31 吴江南玻华东工程玻璃有限公司 一种可钢化高反射镀膜玻璃
CN110770185A (zh) * 2017-04-28 2020-02-07 法国圣戈班玻璃厂 着色窗玻璃及其制备方法
CN110770185B (zh) * 2017-04-28 2022-12-27 法国圣戈班玻璃厂 着色窗玻璃及其制备方法
CN115116342A (zh) * 2022-07-28 2022-09-27 合肥维信诺科技有限公司 盖板及显示模组
CN115745426A (zh) * 2022-11-03 2023-03-07 青岛中兴通轨道交通科技有限公司 一种锂铝硅玻璃的强化方法

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JP5603321B2 (ja) 2014-10-08
EP2262744B1 (fr) 2020-01-08
EP2262744A1 (fr) 2010-12-22
EP3702337A1 (fr) 2020-09-02
PL2262744T5 (pl) 2023-04-11
EA020277B1 (ru) 2014-10-30
PL3702337T3 (pl) 2024-03-04
PL2262744T3 (pl) 2020-10-19
ES2784186T5 (es) 2023-04-24
EP2262744B2 (fr) 2022-12-28
ES2784186T3 (es) 2020-09-23
EP3702337B1 (fr) 2023-10-04
WO2009115596A1 (fr) 2009-09-24
EA201001514A1 (ru) 2011-06-30

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Application publication date: 20110223