CN101980984B - 覆盖有薄层的玻璃 - Google Patents
覆盖有薄层的玻璃 Download PDFInfo
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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。
Description
技术领域
本发明涉及包含一组赋予防阳光或低辐射性能的薄层的玻璃(vitrages)。
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。
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,以其机械耐受性著称的层,尤其是某些以前提出的氧化物,可能难以产生,例如SiO2。至于SnO2,其不具有优异的耐受性。对于这些表面层构成另一种可能性的氮化物需要在氮气气氛下沉积,这限制了使用的可能性。其它的层不能提供令人满意的光透射。
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%。
为了合适地发挥其作用,保护性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。
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锡氧化物层,或者氮化硅或氧氮化硅层。硅阴极可以包含大约4%的低数量的铝作为掺杂剂,它们也存在于该层中。这些层紧接地位于基于钛氧化物的表面层的下面,并且具有也可以是大约几纳米的相对适度的厚度。这些层并且尤其是锡氧化物层,当其厚度明显较大时,也可以在所构成的干涉体系中发挥显著的光学作用。
根据本发明的经覆盖的玻璃有利地具有根据形成标准ASTM2486D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ISO6270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对应于完全没有缺陷的玻璃。对于经受根据标准EN1096的盐雾化测试的样品,结果有利地是在2天暴露后大于3。
附图说明
本发明在还作为附图的主题的下述实施例中被详细地描述,其中:
-图1是覆盖有根据本发明的层体系的玻璃的剖面示意图;
-图2示出了包含两个银层的其它层体系;
-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,尤其是不粗糙。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。
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“隔离(barrière)”或者“牺牲”层,所述气氛在没有这个层存在时可与银层反应。
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,尤其是以下物质的氧化物:钛、包含NiCr的材料、或者Zr,以及相应的低氧化物。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金属的靶开始来形成,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和6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的氧化防构成。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是根据本发明的基于包含高硬度氧化物(ZrO2,SiO2,CréO3)的钛氧化物的层。
作为符合本发明的这种类型的堆积(empilage)的例子,得到下面的样品。厚度以埃表示:
TiZrOx | ZSO9 | Ag | TiOx | ZSO9 | TiZrOx | |
实施例1 | 180 | 60 | 120 | 20 | 210 | 160 |
实施例2 | 180 | 60 | 120 | 30 | 210 | 160 |
在该表中:
-ZSO9意指掺杂有10%重量锡氧化物的锌氧化物层;
-TiOx是低氧化的钛氧化物(任选地,TiOx可以由ZrOx代替,后者是低氧化的锆氧化物);
-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;它从陶瓷靶获得并且在轻微氧化性的气氛下沉积,所获得的层几乎是化学计量的;
下面是对比实施例,其与前述实施例类似但不包含根据本发明的表面层:
TiO2 | ZnO | Ag | TiOx | ZnO | SnO2 | |
对比实施例1 | 200 | 60 | 125 | 30 | 250 | 200 |
TiO2是在有助于形成与隔离层TiOx对比几乎化学计量的化合物的条件下沉积的层,所述隔离层TiOx根据其功能通过保持在之后层沉积过程中减弱或消失的一定亚化学计量进行沉积。
所有这些实施例均对应于“非钢化(non-trempables)”玻璃的低辐射的体系。在经受弯曲/钢化类型的强烈热处理后,它们的光学性质可得到显著改变。
对样品耐受机械试验的能力进行测试。在测试的条件中,在下面的层的构成中显示的差异并不太重要。结果基本上取决于表面层的性质。
根据标准ASTM2486D,使样品经受使用干刷子的测试。测量刮划比率。该比率越低,机械耐受性(résistancemécanique)越好。包含SnO2表面层的样品具有40%的刮划比率。根据本发明的样品1和2分别具有5%和15%的比率。因而,它们的强度得到非常显著的改善。
对以下面方式构成的体系进行了类似测试(厚度用埃表示):
TiO2 | ZnO | Ag | TiOx | ZnO | SnO2 | TiZrOx | |
对比实施例A | 200 | 50 | 120 | 30 | 200 | 250 | |
实施例B | 200 | 50 | 120 | 30 | 200 | 250 | 31 |
实施例C | 200 | 50 | 120 | 30 | 200 | 250 | 63 |
对这些样品而言,CIELAB体系中的光学性能和电阻(résistance)以下列方式来确定:
光透射
Y(D65.2°) | L*(D65.10°) | a*(D65.10°) | b*(D65.10°) | |
对比实施例A | 86.14 | 94.27 | -1.81 | 3.88 |
实施例B | 86.87 | 94.6 | -2.03 | 3.39 |
实施例C | 86.19 | 94.3 | -1.85 | 3.49 |
光反射
Y(D65.2°) | L*(D65.10°) | a*(D65.10°) | b*(D65.10°) | |
对比实施例A | 27.8 | 0.15 | -10.44 | 19.68 |
实施例B | 27.8 | 0.3 | -8.44 | 4.89 |
实施例C | 28.38 | 0 | -9.65 | 5.46 |
确定这三个样品各自的每平方的电阻为3.65、3.44和3.51Ω/□。
光学性质和电阻没有因为本发明的保护性层的存在而明显地改变。根据标准ASTM4086D测得的耐磨性会因为更厚的保护性层而更好。对于在湿法摩擦测试(“wetrubtest”)中的耐剥层性来说也是同样的情况。
“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。
对所谓化学测试的耐受性还显示出随保护性层厚度的改善。进行三种类型的测试。所谓Cleveland、气候室和盐雾的测试。这些测试的性质在下文中关于在包含两个银层的样品上进行的测试作详细说明。具有最厚保护性层的样品还同时显示对这三种测试的最好的耐受性。因此确定相应的值为Cleveland4.5,气候室4.5和盐雾3.5。
用包含两个银层的层体系进行其它测试。再次进行对比测试。对比样品包含锡氧化物的表面层。根据本发明的样品由如前的钛和锆的混合氧化物层所覆盖。
在第一对比中,结构如下(如前,厚度用埃表示):
层 | 9 | 3 | 4 | 5 | 10 | 11 | 4’ | 12 | 13 | 7 |
对比实施例2 | TiO2 | ZnO | Ag | TiOx | TiO2 | ZnO | Ag | TiZrOx | ZnO-Al | SnO2 |
230 | 60 | 95 | 30 | 610 | 60 | 135 | 30 | 120 | 180 | |
实施例3 | TiO2 | ZnO | Ag | TiOx | TiO2 | ZnO | Ag | TiZrOx | ZnO-Al | TiZrOx |
230 | 60 | 95 | 30 | 610 | 60 | 135 | 30 | 90 | 150 | |
对比实施例3 | TiZrOx | ZnO-Al | Ag | TiOx | TiO2 | ZnO-Al | Ag | TiOx | ZnO | SnO2 |
230 | 60 | 95 | 30 | 610 | 30 | 135 | 30 | 100 | 160 | |
实施例6 | TiZrOx | ZnO-Al | Ag | TiOx | TiO2 | ZnO-Al | Ag | TiOx | ZnO-Al | TiZrOx |
230 | 60 | 95 | 30 | 610 | 30 | 135 | 30 | 100 | 160 |
在该表中,缩写具有与前述相同的含义。此外,ZnO-Al意指掺杂有铝的锌氧化物,其包含5%重量的铝。
该结构是在图2中图解说明的结构,其涉及的是对比样品和本发明的样品。
前述样品经受了一系列耐受性测试。
第一个测试涉及根据作为标准ISO6270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,分数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 | 喷雾2天 | UV | |
对比4 | 2.5 | 3 | 4 | 1 |
实施例5 | 4 | 4.5 | 3.75 | 3 |
对比5 | 1.5 | 3.5 | 4 | 3.25 |
实施例6 | 3.75 | 3.5 | 4 | 3.75 |
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。
用基于钛和设有硅的混合氧化物(TiSiO)的表面层进行其它测试。硅氧化物的比率为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。还在不同的表面层厚度(30、80和)下测试了这些结构。
层体系的结构与前述实施例1和2的结构类似。
TiO2 | ZSO9 | Ag | TiOx | ZSO9 | TiSiO |
180 | 60 | 120 | 20 | 210 |
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”测试显示出根据本发明的样品的非常好的耐受性。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:
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。这种耐刮划性也在较少的程度上取决于层的厚度。
相对于具有机械耐受性质的其它类型的层例如氮化钛而言,根据本发明的用作保护性表面层的层还具有对可见波长来说是非常透明的优点。这种透明性因为层的氧化更完全而更好。图3和4说明了这种特性。
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。
根据本发明的表面保护性层有利地用于保护包含一个、两个或三个银层的低辐射体系,每个银层具有7至20nm的厚度。这些体系还包含尤其基于锌氧化物、锡氧化物及它们的合金的介电层。这些体系另外还包含位于银层之上且由钛或NiCr、Zr和其氧化物或低氧化物构成的隔离层。
根据本发明的用作低辐射玻璃的玻璃尤其包含从玻璃片开始的以下结构:
ZnSnO(50/50)/ZnSnO(90/10)/Ag/TiOx/ZnSnO(90/10)/ZnSnO(50/50)/TiZrOx(55/45)。
在这种结构中,基于银的层具有10至14nm的厚度,位于该银层之下的介电层分别具有20至35nm和6至10nm的厚度,并且对于位于银之上的基于锌氧化物的介电层,各自厚度为15至25nm和15至25nm,TiZrOx表面层的厚度为5至8nm。
根据本发明提出了类似的层体系,这次其包含两个基于银的反射层。这种体系的结构从玻璃基材开始是:
ZnSnO(50/50)/ZnSnO(90/10)/Ag/TiOx/ZnSnO(50/50)/ZnSnO(90/10)/Ag/TiOx/ZnSnO(90/10)/ZnSnO(50/50)/TiZrOx(55/45)
其中,对于每组介电层厚度例如是在第一银层之下20至35nm和6至10nm,银层之间对于基于锌氧化物的层各自为8至20nm、40至70nm和8至20nm,以及在第二个银层之上的层为6至10nm和20至35nm,所述银层各自具有10至14nm的厚度,并且TiZrOx表面层的厚度是5至8nm。
在这种结构的基础上,将包含根据本发明的表面保护层的整体与没有这种层的类似结构进行比较。各个层的相应厚度为:
对比实施例
268/110/118/21/685/160/166/23/140/107/105
根据本发明
218/160/118/21/685/160/166/23/120/77/105/31
使样品经受下述测试:
刷子 | Cleveland | 气候室3天 | 喷雾2天 | UV | |
对比 | 75% | 2 | 3 | 4 | 4.5 |
本发明 | 1% | 4 | 4.5 | 4 | 4.5 |
根据本发明的结构显示出非常良好的耐磨性和耐受潮湿条件下的测试的性能。
Claims (16)
1.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一个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,
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;
并且其中钛氧化物占该表面层的至少40%重量,其中该基于钛氧化物的表面层具有16nm~不大于35nm的厚度,并且
其中基于钛氧化物的表面层是TiZrOx层,包含以重量计50%的TiO2,46%的ZrO2,其余由通常伴随锆的成分构成。
2.根据权利要求1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。
3.根据权利要求1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。
4.根据权利要求1的玻璃,其中将该基于钛氧化物的表面层施加于第一保护性层之上,所述第一保护性层是任选地包含Al的硅的氧氮化物或者氮化物或者锡氧化物的层。
5.根据权利要求1的玻璃,其在根据标准ASTM2486D进行的耐刮划性测试中导致至多等于30%的刮划比率。
6.根据权利要求1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。
7.根据权利要求6的玻璃,其包含一个、两个或三个银层,每个的厚度为7至20nm。
8.根据权利要求7的玻璃,其中每个基于银的层覆盖有由NiCr、Ti的氧化物或低氧化物形成的牺牲层。
9.根据权利要求6、7或8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的锌氧化物的层上。
10.根据权利要求1-8中任一项的玻璃,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10%重量。
11.根据权利要求1-8中任一项的玻璃,其中通常伴随锆的成分由氧化物Y2O5构成。
12.根据权利要求5的玻璃,其在根据标准ASTM2486D进行的耐刮划性测试中导致至多等于20%的刮划比率。
13.根据权利要求1至8之一的玻璃,其中所述层体系从玻璃基材开始以下述方式构成:
ZnSnO(50/50)/ZnSnO(90/10)/Ag/TiOx/ZnSnO(90/10)/ZnSnO(50/50)/TiZrOx(55/45)
其中基于银的层具有10至14nm的厚度,并且TiZrOx表面层的厚度为5至8nm。
14.根据权利要求1至8之一的玻璃,其覆盖有包含2个基于银的层的层体系,其中所述层体系具有从玻璃基材开始的下述结构:
ZnSnO(50/50)/ZnSnO(90/10)/Ag/TiOx/ZnSnO(90/10)/ZnSn(50/50)/
ZnSnO(90/10)/Ag/TiOx/ZnSnO(90/10)/ZnSnO(50/50)/TiZrOx(55/45)
基于银的层各自具有10至14nm的厚度,并且TiZrOx表面层的厚度为5至8nm。
15.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。
16.根据权利要求15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。
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