CN1041579A - 整体窗玻璃用低反射性、高色饱和度的涂层 - Google Patents

整体窗玻璃用低反射性、高色饱和度的涂层 Download PDF

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CN1041579A
CN1041579A CN89107561A CN89107561A CN1041579A CN 1041579 A CN1041579 A CN 1041579A CN 89107561 A CN89107561 A CN 89107561A CN 89107561 A CN89107561 A CN 89107561A CN 1041579 A CN1041579 A CN 1041579A
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弗兰克·霍华德·吉勒里
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Abstract

一种反射太阳能的透明制品，包括一层锌/锡氧化物膜，该膜通过干涉效应而显示出颜色，并包括一层反射的金属膜，该膜最好由铬组成以及其制作的一种喷镀方法。

Description

本发明通常涉及在非金属的基体上喷镀含金属的涂层膜的技术，特别是涉及在玻璃上的多层金属/介电的透明膜的磁力喷镀技术。
授与Glber的美国专利3，990，784号披露一种涂层的建筑玻璃系统，包括一个透明基体和一个多层涂层，该涂层包括中间夹着一个介电层的第一和第二金属层，其中第一和第二金属层有一个厚度比，因此只要保持该比率不变，通过改变各金属层的厚度就可改变涂层的透明度，而与其反射性质无关。介电层有一个厚度，因此来自涂层的反射并不强烈地着色。
授与Grubb等人的美国专利4，022，947号披露一种能透过所需要的部分可见射线而反射大部分入射的太阳射线的透明板以及一种制备该透明板的方法。该方法是喷镀一种铁、镍和铬的合金以得到一个透明的金属膜，并在氧气存在的情况下反应性地喷镀上述的或类似的合金以形成一个氧化物膜。在一个优选实施方案中，该金属膜位于基体和金属氧化物膜中间。在另一个优选实施方案中，该金属氧化物膜位于基体和金属膜之间。
授与Hartig等人的美国专利4，534，841号披露一种控制太阳热的窗玻璃，该窗玻璃的制作方法是通过在含氧气氛中的阴极蒸发;首先将一氧化物层施于一个透明基体上，该氧化物层具有20-280nm的光学厚度;其次在由一种惰性气体如氩，和氮气组成的气氛中施加一氮化铬层，该层具有10-40nm的几何厚度;第三光学介电层可施于第二层上。该氧化物层选自锡、钛和铝的氧化物。
由于加热和冷却的能量消费变得越来越昂贵，具有金属的和/或金属氧化物膜的建筑玻璃制品的重要性不断增加。涂层的玻璃建筑制品通常分成两类：太阳能控制的和高透光率、低辐射率的涂层制品。
太阳能控制的玻璃制品通常是玻璃基体，常为着色的，用一种低可见透射性的着色的膜敷盖的，该着色的膜降低太阳能穿过窗进入建筑物内部的透射性，因而降低空调的费用。这些制品在温暖气候中最有效，而最常见于商品建筑物中。在供热的费用有很大关系的那些区域，特别是在居民建筑中，为了使可见光线高度透射进入室内，同时反射红外辐射以保持建筑物内部的热量，高透光度、低辐射率的涂层是理想的。高透光度、低辐射性涂层一般是多层的膜，其中一种红外反射金属如银、金或铜被夹在抗反射的金属氧化物层中间，该金属氧化物如铋、铟和/或锡的氧化物。另一方面，太阳能控制膜一般为一种或多种金属或者金属氧化物的单层膜，所说的金属例如钴、铁、铬、镍、铜等等。
生产一种着色的反射涂层最简单的方法是使用金属的体色。因此镀铜产生一种着铜色的涂层，镀金产生一种着金色的涂层，镀镍产生一种灰色，等等。一种更高级的涂层技术是改良金属颜色或在金属上面通过引入一种吸收着色涂层来造成一种新的颜色。其干涉效应往往是很弱的，但如果造成适当大的或等量的反射来干扰，则该效应可相当强。可通过使用高折射指数的介电质或用金属层增强介电层的反射率做到这一点。这包括使用顺序为金属氧化物介电质/金属的两层或顺序为金属/金属氧化物介电质/金属的三层。
众所周知的膜是具有多样体色的。用湿化学法制造这类太阳能控制的膜公开于美国专利3，846，152;4，091，172;3，723，158和3，457，138好中。当一些真空涂层技术成为商业应用时，那些现存的着色涂层可基本上用与原来那样相同的金属叠涂上去。为制作金属的太阳能控制膜的喷镀技术披露于美国专利4，512，863和4，594，137号。金属涂层的缺点是其缺乏颜色的多样性和亮度，并需要大量的材料和靶序来制造它们。一个理想的新系列涂层应由最小数量的材料提供最多数量的颜色。为达到此目的，干涉色型的涂层是理想的，因为其颜色可通过改变介电层的厚度来改变，而通过改变一个或几个金属层的厚度来改变其透光度和反射率。新系列涂层的其它理想性质是高度饱和的颜色、低反射率和第二表面的整体耐久性;即，该涂层应是坚硬的和化学上耐久的。此外，所使用的材料是便宜的、无毒的和喷镀牢固的。材料的反射颜色通过其光的反射能力分光光度计曲线来描述。大幅度的曲线产生强烈的颜色，而低反射率要求曲线最小值接近于零。第二级的干涉色比第一级强烈，但第三级的干涉色强度变得小些。通常，高折射指数材料产生高反射率或大的曲线幅度。高折射指数的介电材料也使双层涂层具有更强烈的颜色。对于金属/介电质/金属顺序的层来说，似乎是低折射指数的介电材料可得到所期望的结果。由F.H.Gillery于1987年11月25日提出的美国专利系列号125，437披露具有反射饱和色的多层膜，其中锡/锑氧化膜镀是与一种像氮化铬这样一类的金属膜结合而镀上的。该披露的专利以参考文献的形式加入本文。
本发明提供一种新型的高级介电质膜，该膜是用于在玻璃上的各种多层建筑涂层。本发明包括在包含氧的气氛中同时喷镀锌和锡以镀一层包括锌/锡的氧化物涂层。本发明的锌/锡的氧化物膜是与像氮化铬这样一类的金属膜结合而镀上的，以形成一种具有相当饱和色的各种着色多层膜。
本发明提供制作具有最少的层数和材料的一系列着色涂层的能力。本发明的涂层系统具有相当低的反射率、高的色饱和度和整体耐久性。
已知可用围绕一透明介电材料层的第一和第二金属层制成一种颜色系列;通过改变介电质层的厚度可使颜色产生变化。然而，以前所知道的介电材料在高指数折射、牢固喷镀和整体耐久性的必不可少的性能中的一个或多个是有缺陷的。本发明的锌/锡的氧化物则具有上述的性能，以及与适宜的金属膜结合能产生强烈着色的建筑涂层。例如，与一种铬基的膜相结合的锌/锡氧化物可用于制作具有优良耐久性的一个范围的有吸引力的颜色。
用反射循环图和计算机计算，确定一个金属和介电质的两结合层对两层都具有最佳的厚度，该层提供最小的反射和最高的色饱和的组合。介电质的折射指数愈高，最佳的涂层透射性愈低，而色饱和度愈高。具有低n和高k（其中n和k为综合折射指数的有效部分和综合部分，确定电磁辐射在介质中传播）的金属趋向于提供最低的透射性和最高的饱和度。
如果为了降低透射性增加金属的厚度，则反射性增加而色强减弱。在介电质层镀覆以前镀上一个薄金属层可降低反射性并得到更强的饱和色。如果在与非常薄的金属镀层相结合时最初的金属层厚度增加了，则可制成一种低透射、低反射、高度着色的涂层。如果使用二个最初的金属层，则与一低n、高k的金属相结合的低折射指数介电质提供最吸引人的外观。计算表明，用一种与具有折射指数为2.3的介电质结合的金属，在20%的透光率下，可得到足够的饱和度。大于对于一种较低折射指数的介电质来说，金属-介电质-金属体系是最优的。
用本发明的锌/锡的氧化物，许多金属或金属合金膜可用于提供具有优良性质的多层涂层。优选的膜包括像铬这样一类的金属，像轻微氧化的铬和最好是氮化铬这样一类的金属涂层。其它优选的金属膜包括钛和氮化钛以及金属合金如不锈钢和镍合金如铬镍铁合金。
在传统的磁控喷镀工序中，将一个基体放在一个涂层小室中，面向具有要喷镀的材料的靶面的阴极。按照本发明优选的基体有玻璃、陶瓷和塑料，它们不受涂层工序的操作条件有害影响的。
该阴极可以是任何传统形状的，最好是细长矩形的形状，与电势接触，并最好采用与一磁场相结合，以增强喷镀工序。阴极最好是如Gillery等人的美国专利4，478，702中所述对称形状的并且定位装成的组件。其披露内容以参考文献的方式并于本文。
将一透明玻璃基体置于一真空的涂层小室中，将小室抽真空，最好抽到低于10-4乇，更好的是低于2×10-5乇。将一种选择的活性气体气氛（最好是氩和氧）在小室内形成约5×10-4到10-2乇之间的压力。在整个基体表面上操作具有锌和锡靶面的阴极。溅射靶金属，与小室中的气氛反应而在玻璃表面镀上一个锌/锡的氧化物涂层。
在镀涂锌/锡氧化物初始层之后，将涂层小室抽真空，然后装入一种惰性气氛如纯的氮，造成约5×10-4和10-2乇之间的压力。在锌/锡氧化物涂镀的表面上面操作具有金属或金属合金（最好是铬靶面的阴极。对靶进行溅射以在锌/锡氧化物镀涂的玻璃表面上镀一个金属层。按照本发明，铬金属和轻微氧化状态的铬是有用的，氮化铬是最好的。然而钛、氮化钛、不锈钢和镍合金也产生适宜的膜。
在本发明的大多数优选的实施方案中，将金属膜镀在锌/锡氧化物膜的下面以及上面。在两层膜的情况下，来自未涂镀表面的反射的颜色主波长几乎完全取决于锌/锡氧化物层的厚度。使顶部金属层的厚度进行变化，直到透射率接近于所要求的数值为止，然后使底下的金属层厚度进行变化，直到从制品未涂镀一面达到理想的反射率为止。需要对顶部金属膜厚度的最终改良以得到最佳的最终透射率。在有意义的厚度范围内，增加顶部金属膜的厚度来降低透射性而增加来自涂层制品未涂镀面的反射性。在有意义的厚度范围内增加底部金属膜的厚度，来增加透射性而降低来自未涂镀一面的反射性。
涂层从介电层的干扰作用得到它的颜色，这取决于介电层的厚度。按照本发明的氮化铬-锌/锡氧化物-氮化铬膜是特别吸引人的深兰色型。锌/锡氧化物层最好通过溅射锌/锡合金阴极来镀涂。锌和锡的比例最好每种在10和90%之间，更好的是30-70%的锡，其余是锌，而最优选的则是锌和锡各约50%。
实例1
在下述条件下，在一个玻璃基体上镀涂锌/锡氧化物和氮化铬的多层涂层。将洁净玻璃基体保持在纯氮气氛的真空小室内，压力为2.2毫乇。用在377伏特7.5瓦下驱动的阴极，一个尺寸为15×106英寸（约0.4×2.7米）的铬靶和100英寸/分钟（约2.54×2.7米/分钟）的线速度，镀成一个35
Figure 891075615_IMG1
厚的氮化铬层，降低玻璃的透射性到70%。由四个50/50锌/锡靶在320-340伏之间的电压下，总功率为76kw，在50/50氩/氧气氛中，其压力为3毫乇，以及同样的玻璃速度运行而施加该氧化层。该透射率由锌/锡氧化物层降低到58%。由在492伏和54瓦下激发的单个铬阴极在3毫乇的纯氮气氛中镀成最终的氮化铬层。在同样的玻璃速度下，一次镀涂降低透射率到22%。该深层具有深兰的颜色，色度坐标为y＝9.28，x＝0.2325，而来自未镀涂玻璃表面的反射率的y＝0.2460。该涂层极其硬，在Taber研磨机上经受CS10F轮的80循环研磨时，其透射性只增加1.6%。该涂层还能经受住在30%硝酸或20%盐酸中浸渍没30分钟，在150°F（约66℃）下经Cleveland（雾化湿度）试验至少一个月，以及用5%的盐喷射1个月。
实例Ⅱ-ⅩⅡ
对于这些实例，如前述实例一样，在纯氮气中镀氧化铬膜和在50/50氩/氧中镀锌/锡氧化物膜。下表所示为每层镀膜后的透射性，以及根据色度座标表示的反射颜色和从涂层制品的未涂敷的玻璃表面肉眼观察颜色。
实 第一层Zn/Sn 第二层 R2（第二层表面 颜色
例    CrN    CrN    反射性）
%T    %T    %T    Y    X    Y
Ⅱ    78    71    17    13.7    .2437    .2633    淡兰
Ⅲ    64    64    16    10.7    .2246    .2397    兰
Ⅳ    58    62    17    9.2    .2236    .2342    深兰
Ⅴ    46    54    18    10.5    .2356    .2464    兰
Ⅵ    38    47    16    13.6    .2592    .2745    淡兰
Ⅶ    58    62    17    11.2    .2261    .2459    绿-兰
Ⅷ    58    61    17    7.5    .2259    .2260    红-兰
Ⅸ    59    61    17    6.5    .2325    .2249    红-兰
Ⅹ    63    63    18    5.9    .3339    .3065    紫-粉
Ⅺ    77    70    18    11.7    .3714    .3766    橘-黄
Ⅻ    63    62    18    9.2    .3802    .3788    深橘-黄
提供以上各实例用以说明本发明。各种各样的含金属层可用于本发明的锌/锡氧化物电层的一面上或两个面上，厚度范围可以很宽，取决于所要求的透射性和反射性诸性质。该锌/锡氧化物介电膜本身的厚度可加以变化，来产生所要求的颜色。像压力、气氛、功率、电压线速度等等这样一类的喷镀参数的范围取决于所采用的喷镀装置和所要求的产量。本发明的范围以下述权利要求书规定之。

Claims (21)

1、一种制造反射太阳能的制品，包括：
a.一个透明的基体；
b.一种镀在所说的基体表面上的锌/锡氧化物的透明膜，其厚度由干涉效应显示出颜色；
c.一种镀在所说的锌/锡氧化物膜上的反射透明金属膜；
2、按照权利要求1所述的制品，其中的基体是玻璃。
3、按照权利要求2所述的制品，其中的反射金属膜包括一种选自铬、钛、不锈钢和镍合金中的金属。
4、按照权利要求3所述的制品，其中的反射金属膜选自铬金属、氧化铬、氮化铬、钛金属、氮化钛、不锈钢和铬镍铁合金中。
5、按照权利要求4的制品，其中的反射金属膜是氮化铬。
6、按照权利要求1的制品，还包括一个第二层透明反射金属膜，该膜镀于基体和锌/锡氧化物膜之间。
7、按照权利要求6的制品，其中的第二层透明反射金属膜包括一种选自铬、钛、不锈钢和镍合金中的金属。
8、按照权利要求7的制品，其中所说的第二层金属膜选自铬金属、氧化铬、氮化铬、钛金属、氮化钛、不锈钢和铬镍铁合金中。
9、按照权利要求8的制品，其中所说的第二层金属膜是氮化铬。
10、按照权利要求1的制品，其中所说的锌/锡氧化物的透明膜的厚度足以使涂层制品显示出一种兰色干涉色。
11、一种制作太阳能反射涂层制品的方法包括以下步骤：
a.在一基体表面上喷镀锌/锡氧化物的第一透明涂层，由干涉色显示出颜色;以及
b.在整个所说的锌/锡氧化物膜上喷镀一层反射的透明金属膜。
12、一种按照权利要求11的方法，其中所说的基体是玻璃，而所说的喷镀是磁力增强的。
13、一种按照权利要求12的方法，其中所说的金属膜由喷镀一种金属而镀涂，该金属选自铬、钛、不锈钢和镍合金中。
14、一种按照权利要求13的方法，其中是在一种惰性气氛中溅射铬以镀涂出铬金属。
15、一种按照权利要求13的方法，其中的铬是在一种氧化气氛中进行溅射，镀涂出的铬处于轻微氧化的状态。
16、一种按照权利要求13的方法，其中的铬是在纯氮的气氛中进行溅射，以镀涂出氮化铬。
17、一种按照权利要求11的方法，其中的一层透明金属膜是在溅射锌/锡氧化物涂层之前镀涂在基体上的。
18、一种按照权利要求17的方法，其中所说的透明金属膜是在用溅射铬以镀锌/锡氧化物膜之前镀涂在基体上的。
19、一种按照权利要求18的方法，其中所说的铬是在一种惰性气氛中进行溅射，以镀涂出铬金属。
20、一种按照权利要求18的方法，其中的铬是在一种氧化气氛中进行溅射，以镀涂出轻微氧化的铬。
21、一种按照权利要求18的方法，其中的铬是在纯氮的气氛中进行溅射，以镀涂出氮化铬。
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CN101805132B (zh) * 2010-03-26 2012-11-28 洛阳新晶润工程玻璃有限公司 一种用于提高可钢化低辐射镀膜玻璃耐高温的方法
CN104691028A (zh) * 2015-03-20 2015-06-10 武汉理工大学 一种高反射隔热层材料及其制备方法
CN108645062A (zh) * 2018-04-18 2018-10-12 华中科技大学 一种太阳能集热膜

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EP0363747B1 (en) 1999-06-16
AU605047B2 (en) 1991-01-03
JPH02145458A (ja) 1990-06-04
DK484089D0 (da) 1989-10-02
DE68929017D1 (de) 1999-07-22
EP0363747A1 (en) 1990-04-18
AU3997589A (en) 1990-04-05
FI103503B1 (fi) 1999-07-15
DK172969B1 (da) 1999-10-25
JP2604474B2 (ja) 1997-04-30
NO893634D0 (no) 1989-09-11
KR920005650B1 (ko) 1992-07-11
NO893634L (no) 1990-04-04
NZ230494A (en) 1992-04-28
CN1019098B (zh) 1992-11-18
NO174845C (no) 1994-07-20
FI103503B (fi) 1999-07-15
DK484089A (da) 1990-04-04
CA1337057C (en) 1995-09-19
ZA896264B (en) 1991-04-24
US5112693A (en) 1992-05-12
DE68929017T2 (de) 2000-01-05
FI894511A (fi) 1990-04-04
KR900006250A (ko) 1990-05-07
NO174845B (no) 1994-04-11
ATE181310T1 (de) 1999-07-15
GR3031228T3 (en) 1999-12-31
FI894511A0 (fi) 1989-09-25

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