CN1671632A - 用于玻璃板适合于预加应力的层系统 - Google Patents

用于玻璃板适合于预加应力的层系统 Download PDF

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CN1671632A
CN1671632A CNA038185091A CN03818509A CN1671632A CN 1671632 A CN1671632 A CN 1671632A CN A038185091 A CNA038185091 A CN A038185091A CN 03818509 A CN03818509 A CN 03818509A CN 1671632 A CN1671632 A CN 1671632A
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layer
zno
layer system
sacrificial metal
tectum
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H·施希特
L·伊洛
U·施密德特
H·辛德勒
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3626Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3652Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
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    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3602Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
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Abstract

一种具有低发射率,适合于被烧结施加预应力,用于玻璃板,具有作为功能层的银的层系统,它含有Ti或Ti与Zn和/或Al的合金,位于银层下面的金属牺牲层、抗反射介电层和氧化物、氮化物或氧氮化物的覆盖层。该金属牺牲层含有化学结合的氢。任选掺杂有Al和/或In的ZnO层与金属牺牲层相邻。该覆盖层由钛化合物构成。此类层系统能够通过比较经济的方法制造,具有很高的耐久性和高耐化学性能。即使在高温下进行热处理的情况下,其色度参数也能够很好地再现。

Description

用于玻璃板适合于预加应力的层系统
本发明涉及玻璃板用的具有作为功能层的银层、位于此银层上面的牺牲层、抗反射的介电层和氧化物、氮化物或氧氮化物覆盖层的层系统,该层系统具有低的发射率,适合于强的热激发(sollicitéthermiquement)。
当此被涂布的玻璃板受到弯曲和/或施加预加应力的操作时,此低发射率层系统应该能够被强烈地热激发。当然,当玻璃板只是在弯曲和施加预应力之后涂布,热稳定的层并非是必需的,它表现出并非总能够避免缺少涂层的缺点。这样的缺少是由于热处理操作经常造成玻璃表面发生局部变化而产生的,而在涂布以后这种局部变化就可以看到了。特别是,由于能够涂布大型工业装置上的大玻璃板,因此进行了热处理的涂层还具有使涂布操作简化的经济上的优点。然后切割成以常用方式涂布和弯曲和/或预加应力的大玻璃板所希望的形状。
此适于强热激发的层系统已知各种实施模式。在第一组适合于强热激发的层系统中,抗反射层是由Si3N4构成的,它们由CrNi金属牺牲薄层与银功能层分开。例如,在文献EP0,567,735B1、EP0,717,014B1、EP0,771,766B1、EP0,646,551B1和EP0,796,825A2中叙述过具有此结构的层系统。在EP0,883,585B1中叙述的层系统也属于这一组,但在此情况下,金属牺牲层是由Si构成的。当然,这些层系统是非常热稳定的,由于在氮化物雾化时所存在的已知问题,使得它们制造很昂贵。另外,由于在层中的机械应力,使得比较厚的Si3N4层的雾化仍然是个问题。
属于第二组适合于强热激发的层系统,除了比如Si3N4或AlN以外,特别是在覆盖层区域内还具有氧化物层。比如DE196 40,800C2叙述了例如一种层系统,在此层系统中,在紧固金属层和氧化物或氮化物覆盖层之间具有金属牺牲层金属的氮化物或氧氮化物中间层。由DE101 05,199C1中已知的另一种此类层系统,其特征在于,在银层和金属牺牲层之间具有Si3N4或AlN层。在由EP0,834,483B1已知的层系统中,在由Ti制造的金属牺牲层和覆盖层之间具有厚度至少5nm的TiO2中间层,而在此中间层上设有由Bi、Sn、Zn或这些金属混合物的氧化物、氮化物或氧氮化物制造的覆盖层。无论Si3N4或A1N中间层,还是TiO2厚层制造起来都是很复杂的。另外,具有高折射率的TiO2厚层对层厚的均匀性都有很高的要求,在厚度上已有的很小偏差,在施加预应力的操作以后都可能导致色度的误差。
在适合于强热激发的第三组层系统中,除了功能层和金属牺牲层以外,单个的层由纯氧化物层构成。作为氧化物层,在大多时候雾化没有问题,这种层系统制造起来也是经济的。但是,在此情况下,金属牺牲层的厚度比较厚。在比如DE198 52,358C1中叙述了此类层系统。在此情况下,牺牲的金属是由铝与如下一种或几种作为合金组分的元素构成的合金组成:Mg、Mn、Cu、Zn和Si。
在EP0,233,003B1中,还叙述了用于应该适合弯曲和/或施加预应力操作的玻璃板的纯氧化物层系统。在此已知的层系统中,在银层的上面具有Al、Ti、Zn或Ta的厚度4~15nm的层。优选,Al、Ti、Zn或Ta层也可以在银层的下面。
在DE39 41,027C2中叙述了能够适应弯曲和/或施加预应力的氧化物层系统。在此已知的层系统中,在银层的下面设有厚度最多15nm的ZnO层,覆盖此银层的是钛、铝、不锈钢、铋、锌等牺牲金属的氧化物或这些氧化物的混合物,它们是通过沉积牺牲金属,再将其转化为其氧化物而形成的。
在进行玻璃板的弯曲和/或施加预应力所必需的热处理之后,所有这些已知的层系统的反射色度都会发生或多或少可以察觉的改变,此外按照一般的规律,在热处理以后,其发射率会增大,光线漫射的比例也会增加。由于反射色度的变化,用裸眼就能够识别出引入同一面上没有进行过热处理但具有同样层结构的经过涂布过的和进行过热处理的玻璃板。为此,应该有另一种适合于施加预应力的层系统,其中它们的性能与没有经过热处理的层系统是相当的。
要同时遵守3个重要的条件,即保持限定得很窄的反射色度,以及如果可能,通过热处理操作漫射光比例和发射率没有任何增加,或者只增加很少,这是很难达到的,更加需要中性色度的层系统。
因此,基于本发明的问题包括研制具有主要是氧化物抗反射层的中性色度的层系统,如在进行玻璃板的弯曲和/或施加预应力所必需的热处理操作以后,还具有反射上与预定氧化物的和未进行热处理的层系统基本相同的色度参数,而且其中热处理所增加的漫射光比例和发射率也尽可能很小。同时,此层系统还应该具有很高的耐久性和很高的耐化学性能。
按照本发明,通过使金属牺牲层由Ti或Ti与Zn和/或Al的合金构成,而且含有通过化学结合的氢,再通过任选掺杂了Al和/或In的ZnO层连接着金属牺牲层,再通过覆盖层由钛化合物构成以解决此问题。
具有按照本发明结构的层系统能够相对经济地制造,而且具有高的耐化学性能。而特别是其特征在于,同样在高温下进行热处理,其颜色特征的变化能够受到控制并且可以重现,另外其漫射光的比例只有很小增加,并且发射率很小。
确定无疑地,在Ar/H2工作气体气氛下雾化的金属牺牲层组合物起着特殊的作用。正如金属Ti具有束缚氢的能力,“氢缓冲”还原剂增强了金属牺牲层对银层的保护作用。借助于适当的分析方法能够检测出金属牺牲层中的氢。
例如,含有50~80wt%的Ti和20~50wt%Al的钛合金显示出特别适合于牺牲层。
任选掺杂有Al或In的ZnO层直接放置在金属牺牲层上十分有助于得到所希望的结果。此ZnO层的厚度可以具有比如与其所构成的抗反射层同样的厚度,使得覆盖层直接在此ZnO层之后。但是,还可以只是将ZnO层设计得比较薄,此时它涉及作为抗反射层的部分层,而它所连接的那部分抗反射层是由比如SnO2组成的。但是在此情况下,ZnO层的厚度必须达到至少3nm。
此层系统的覆盖层优选是具有尖晶石结构的混合氧化物,但也包括Ti/Al型二元合金。对于覆盖层来说,下面的化合物是特别适当的:ZnO:Al/TiO2、ZnO:Al/Ti、ZnxSnyOz/TiO2、ZnxSnyOz/Ti、ZnxTiyAlzOr、TixAlyOz、TixAly、TixAlyNz、TixAlyOzNr、ZnxSnySbzOr/TiO2、ZnxSnySbzOr/Ti或ZnxSnyAl2Or/TiO2。正如同在此涉及到的钛合金一样,这表示在进行热处理操作之前在它们转化为氧化物形式的过程中的状态,
此层系统的金属牺牲层和其它层的优选组成以及单个层厚度的优选范围显示在所附的权利要求中。
下面借助于实施例更详细地叙述本发明,并将其与先有技术的比较例进行比较。为了评价各个层的性能,对涂布的玻璃板进行了如下的测量和测试。
A测量被涂布的玻璃板在550nm处的透射率T;
B.测量在实验室系统中的反射色度参数(DIN 5033)和使用ISO 0标准作为参考色度。应该将按照如下方式限定在此处所涉及的在预加应力状态下层系统的公差Δ固定值保持为此参考标准色度的参数范围内:
ΔL=±3.0;Δa=±1.4;Δb=-3.5~+1.0;
C.借助于设备FPP 5000 Veeco Instr.和手动测量设备SQO HM-1测量表面电阻率;
D.使用设备Sten Lfving MK2测量发射率E;
E.按照DIN 50017用目视评估在水中进行返潮测试;
F.进行电化学电阻测量(EMK测试),在Z.Silikattechnik 32(1981)第216页中叙述了此测试。此测试能够对位于银层上面的覆盖层的钝化质量和对于Ag层的腐蚀作用做出结论;
G.按照ASTM 2486用目视评估进行Erichen洗涤测试;
H测量划痕硬度,以一定的速度在一个层上拖拉加上重量的一个针。在划出可见划痕下的重量g作为划痕硬度的度量;
I.用Gardner公司的漫射光测量设备测量漫射光,单位是%。
对比实施例
在一个连续的工业涂布装置上,借助于在浮法玻璃上保持磁场的活性阴极雾化法,对如下所述的先有技术(D 39 41,027)的层系统进行涂布,每次以nm为单位给出单层的厚度:
玻璃/3TiO2/22SnO2/13ZnO:Al/12Ag/5TiAl/20SnO2/10TiO2
ZnO:Al层是在反应条件下从含有2wt%Al的金属ZnAl靶被雾化的。金属牺牲层是从含有64wt%的Ti和36wt%的Al的金属靶被雾化的。覆盖层是通过从金属钛靶进行活性雾化而沉积上的。
对多个热处理前的试样进行上述测试,给出如下的平均数值:
A.透射率 T550=76~77%
B.色度参数 ΔL-0.1Δa 4.47Δb-5.31
C.表面电阻 R=6.8~6.9Ω
D.发射率 E=7.8
E.在水中回潮测试 红色斑点
F.EMK测试 140mV
G.洗涤测试 在350次以后层开始剥离
H.划痕硬度 60~210g
I.漫射光 0.17%
将多个尺寸为60cm×80cm不同的被涂布试样在680~700℃下加热,通过急剧冷却施加预应力。然后在此预加应力玻璃上进行后面的测试和测量。不进行水中回潮测试、EMK测试、洗涤测试和划痕硬度测试,因为通过经验可以知道,在热处理操作以后,这些数值不会劣化。进行的测试给出如下的结果:
A.透射率 T550=88.5%
B.色度参数 ΔL1.3Δa1.56Δb-3.95
C.表面电阻 R=4.0~4.6Ω
D.发射率 E=5.8~6.8%
I.漫射光 0.35%
在热处理之后,漫射光的比例从0.17%增加到0.35%,这是允许的。但是,5.8~6.8%的发射率对于制造k值为1.1W/m2K的隔热玻璃板来说是太大了。在施加预应力以后的色度参数位于容许限以外。在弯曲时的玻璃板具有淡蓝红色的外观。不同层之间很宽的厚度偏差更加不允许得到具有目标色度值的中性颜色反射色度。
制造实施例
为了沉积金属牺牲层和为了沉积覆盖层,使用由64wt%的钛和36wt%的铝组成的金属靶,在与比较例同样的涂布装置上制造按照本发明的如下所述层系统。
玻璃/25SnO2/9ZnO:Al/11.5Ag/2TiAl(TiHx)/5ZnO:Al/33SnO2/3TixAlyOzNr
在Ar/H2(90/10vol%)工作气体混合物中进行金属牺牲层的沉积,在Ar/N2/O2工作气体混合物中进行氧氮化物覆盖层的沉积。
在热处理前对涂布玻璃板进行测量和测试给出如下的数值:
A.透射率 T550=78.3%
B.色度参数 ΔL-0.9Δa2.80Δb-3.8
C.表面电阻 R=5.7Ω
D.发射率 E=6.6~6.7%
E.在水中回潮测试 无缺陷
F.EMK测试 -64mV
G.洗涤测试 在1,000次以后没有损伤
H.划痕硬度 150~260g
I.漫射光 0.18%
在预加应力后,对多个样品进行与对比实施例的预加应力的玻璃板相同的测量和测试。这些试验的结果如下:
A.透射率 T550=88.3%
B.色度参数 ΔL1.0Δa1.2Δb-2.4
C.表面电阻 R=3.6-4.0Ω
D.发射率 E=4.8-5.0%
I.漫射光 0.27
对于未经热处理的层还是经过热处理的层,得到的数值都表明有了明显的改善。特别是,经过热处理的层满足预先确定的色度参数。与在比较例中相比,反射色度更加呈中性。在表面电阻和发射率之间的函数依存性很好地相当于物理依存性,能够制造出k值为1.1W/m2K的隔热玻璃板。与比较例相比,通过热处理以后漫射光的比例增加不多。这表明Ag层只受到轻微的破坏。其它测试的结果,比如水中回潮测试、EMK测试、洗涤测试和划痕硬度测试,对未经热处理试样进行的测试都好于平均值。在工业涂布装置上能够稳定地和重现地制造出此层系统。

Claims (8)

1.一种层系统,其具有低的发射率,适合于强热激发的玻璃板用的具有作为功能层的银层、位于此银层上面的金属牺牲层、抗反射的介电层和氧化物、氮化物或氧氮化物覆盖层,其特征在于,该金属牺牲层由Ti或Ti与Zn和/或Al的合金构成并含有化学结合氢,其特征还在于,任选掺杂有Al和/或In的ZnO层连接着金属牺牲层,其特征还在于,该覆盖层由钛化合物构成。
2.按照权利要求1的层系统,其特征在于,该金属牺牲层由含有20~50wt%的铝的TiAl合金构成。
3.按照权利要求1或2的层系统,其特征在于,该金属牺牲层的厚度为1~5nm。
4.按照权利要求1~3的层系统,其特征在于,该ZnO层含有0.5~10wt%的Al和/或In。
5.按照权利要求4的层系统,其特征在于,该ZnO层的厚度为至少3nm。
6.按照权利要求1~5中之一的层系统,其特征在于,SnO2、Si3N4、ZnO、Al2O3和/或SiO2的层被布置作为在ZnO层和覆盖层之间的抗反射表面介电层的部分层。
7.按照权利要求1~6中之一的层系统,其特征在于,该覆盖层由ZnO:Al/TiO2、ZnO:Al/Ti、ZnxSnyOz/TiO2、ZnxSnyOz/Ti、ZnxTiyAlzOr、TixAlyOz、TixAly、TixAlyNz、TixAlyOzNr、ZnxSnySbzOr/TiO2、ZnxSnySbzOr/Ti或ZnxSnyAlzOr/TiO2构成。
8.按照权利要求1~7中之一的层系统,其特征在于以下的层结构:玻璃-SnO2-ZnO:Al-Ag-TiAl(TiHx)-ZnOAl-SnO2TixAlyOzNr
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