CN1157806A - 匹配的、可热处理的、耐久的、不反射的溅射镀膜玻璃及其制造方法 - Google Patents

匹配的、可热处理的、耐久的、不反射的溅射镀膜玻璃及其制造方法 Download PDF

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CN1157806A
CN1157806A CN96121374A CN96121374A CN1157806A CN 1157806 A CN1157806 A CN 1157806A CN 96121374 A CN96121374 A CN 96121374A CN 96121374 A CN96121374 A CN 96121374A CN 1157806 A CN1157806 A CN 1157806A
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S·L·拉森
K·W·哈蒂格
P·J·林格尔
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Abstract

一种溅射镀覆的镀层体系，包括一层位于两层具有要求厚度的Si3N4镀层之间的不氮化和不氧化的镍或镍合金镀层，可用于建筑用和汽车用玻璃基体，从而成为可热处理的，并且具有足够低的ΔE性能而使产品是可匹配的，即在镀有同样镀层的热处理产品和未热处理产品之间是可匹配的。

Description

匹配的、可热处理的、耐久的、不 反射的溅射镀膜玻璃及其制造方法
本发明涉及溅射镀膜玻璃及其制造方法。更具体地说，本发明涉及可热处理并耐久的、且在热处理过程中玻璃一侧的外观没有显著变化的溅射镀膜玻璃。
本申请是1995.6.7提出的申请序号为08/486,643的申请的部分继续申请，而08/486,643号申请是1993.8.5提出的申请序号为08/102,281的申请的部分继续申请。
在建筑设计及汽车设计中使用通用的金属及金属氧化物镀膜玻璃是公知的。正如专利文献及其它文献中多次记载的，通过控制镀膜的层体系，这类玻璃通常可得到非常适宜的反射率、透射率、辐射率、耐化学性、耐久性以及所希望的颜色。在这方面，参见例如美国专利3,935,351、4,413877、4,462,883、3,826,728、3,681,042、3,798,146和4,594,137，这里仅举出了一少部分。
另外已广泛报道过，尽管有一些合理的可接受的用于镀覆这类镀层的工艺，但其中最有效的并因此而最优选的一种是称为“磁性增强溅射镀膜”的公知工艺。这种工艺记载于美国专利4,166,018中，其主题讲授了公认的基本原则。(也可参见Munz等人的((现代建筑玻璃镀膜的性能及溅射规范》SPIE 325卷，“光学薄膜”，1982年，65-73页。)
近年来，通用的镀膜玻璃已被进行过无数次尝试以得到一种镀膜玻璃制品，该制品可在热处理前被镀膜，此后可被热处理而不会使镀层或玻璃自身(即所得的玻璃制品)的性能产生不利的变化。理由之一是，例如，很难在一片已弯曲的玻璃上形成均匀的镀层。已知如果能镀覆一块平板玻璃表面然后弯曲，则为获得均匀镀层所采用的工艺比先使玻璃弯曲所用的工艺要简单得多。同样实际的是，在下述方面，例如，在建筑用及住宅用玻璃的方面，在某些情况下，回火和未回火的玻璃片被用在同一建筑物上，而且至少在玻璃一侧的外观方面就颜色和反射率而论必须尽可能地匹配，这种性能最好用ΔE表示，ΔE是由ASTM规定D-2244-93(1993年11月出版)中题为“根据仪器测量的色坐标计算色差的标准测试方法”所定义的。简言之，ΔE越低越匹配。
过去已经研究出某些工艺以制成可热处理的镀膜玻璃制品，该制品可接着或之后通过回火、弯曲、或一种称为“热强化”的工艺而被热处理。一般说来，许多这种已有的镀膜制品都不能在较高的高温下进行热处理，而这种温度是达到经济的弯曲、回火、和/或热强化(即1150°F-1450°F)所必需的。简言之，这种工艺常常需要将温度保持在大约1100°F或更低，以获得可热处理性而不会对镀层或其基体产生不利影响。即使认为是可热处理的，实际上在公知的已有技术中，用上述体系镀覆的基体在经过热处理后并非真正地与其自身匹配，例如，受到至少在玻璃一侧反射率性能的ΔE值过高的影响。
对镀层或其基体不存在任何本质的不利影响，其含义在这里用术语“可热处理”表示。然而在某些情况下一些性能会在热处理过程中稍有改变，这里所用的“可热处理”是指尽管镀膜玻璃经过了一种或多种上述热处理(即弯曲、回火和/或热强化)，最终的镀层体系和全部产品仍必须达到所希望的性能，如辐射率、薄膜电阻、耐久性和耐化学性。对本发明要得到的大多数建筑用途来说，合适的热处理性是指热处理之前的产品与热处理后的最终产品相比，玻璃以及其上保留的镀层至少在辐射率、薄膜电阻、耐久性和耐化学性方面基本上没有改变。对大多数汽车以及建筑的用途来说，由于可以承受热处理甚至希望进行热处理，辐射率变得更好(即降低)，只要合适的热处理性是指穿过基体发生均匀的改变而且这种改变不依赖于进行热处理所采用的参数。
本发明的实施方案中，镀层体系优选为“可热处理”的，该术语的含义在前述范围内，但同样重要的是，用这种镀层体系镀覆的制品在热处理后仍与未经热处理的同类制品(例如热处理前的该制品本身)相匹配，这是因为至少就玻璃一侧的反射率而论，作为镀层体系性能的ΔE缩小了(即由于本发明的某些镀层体系的独特性)。
在这方面，美国专利5,188,887公开了某些属于已有技术的可热处理的镀层体系，因为尽管所述镀层体系经过了回火、弯曲或热强化，仍能在较高的前述高温下进行成功的热处理，从而达到所希望的结果。一般说来，这些属于已有技术的镀层成分的独特性在于其镀层体系中采用了高镍含量的合金作为金属镀层，该合金的优选是一种称为Haynes 214的合金，基本上由75.45％Ni、4.00％Fe、16.00％Cr、0.04％C、4.50％Al、和0.01％Y(重量百分比)组成的。通过采用高镍含量合金如Haynes 214，并用理想配比的二氧化锡(SnO2)或该二氧化锡与其它镀层(如上述理想配比的二氧化锡底层和/或位于SnO2顶层及高镍含量合金层之间的铝中间层)对其进行表面镀覆，发现玻璃制品的可热处理性可达到在约1150°F-1450°F的高温下停留约2-30分钟，而颜色、机械耐久性、辐射率、反射率或透射率基本没有降低。因此这些成分构成了对已有的可热处理系的显著改进，所述的已有的可热处理体系如公开于以下专利中的那些：4,790,922、4,816,034、4,826,525、4,715,879、和4,857,094。然而，这类镀层体系存在前述不匹配的现象，并通过其热处理所得出的相当高的ΔE表现出来。
除了公开于上述专利中的以上内容外，Leybold防风玻璃体系TCC-2000也是已知的。该体系中，采用了四层或五层金属和金属氧化物以得到溅射镀膜玻璃，这种玻璃在高达1100°F的温度在某种程度下是可热处理的，只要将热处理限制在短时间内，就可用作制造弯曲或未弯曲防风玻璃的预镀覆玻璃。从玻璃基体向外的镀层通常包括第一层氧化锡、第二层镍/铬合金(通常约80/20)、第三层银、第四层镍/铬合金、和第五层氧化锡。除了热处理的温度和时间的上限值相当低以外，所得镀层还相当软，并显示出不合格的低耐化学性以至于实际上只能用于层状防风玻璃的内表面。这些体系没有达到可匹配性。
在上述美国专利4,715,879中，特别指出除非形成金属氧化物(例如氧化锡)保护层以使氧化物缺氧(即不是理想配比的)，否则不能产生镀层体系。当然，这需要在制造过程中准确的平衡。在这方面，可热处理性也公开于美国专利4,826,525中。然而该专利中专门指出必须镀覆铝层以达到可热处理性。但两种情况都没有达到可匹配性。
在上述美国专利5,229,194中，公开了一种甚至与美国专利5,188,887中公开的相比具有显著进步的可热处理溅射镀层。在US5,229,194的发明中发现，如果金属镍或高金属镍含量合金层被分离的镍或者高镍含量合金的氧化物或氮化物层底层和面层所包覆，并且还使用了氧化物如SnO2、ZnO、TiO2或其合金氧化物的另一面层，就可使可热处理的溅射镀膜玻璃达到极好的结果，尤其当这种玻璃被用作汽车的“隐避”窗时。上述发明还提出可用硅作为含镍金属镀层的第一面层。
具有优选构成的这种镀层体系尤其被证明是可热处理的而且是耐磨的。然而，尽管一开始时发现其中一些是耐化学性的，但发现投入批量生产时某些体系通不过相当严格的5％沸腾HCl耐化学性试验(以下论及)。然而发现其红外线及紫外线反射性对于广泛的应用而言是优异的。但是一步讲，对于“隐避”窗用途而言，希望其可见光透射率值低，尽管如此，该值还是被证明过低以至于实际上不能作为需要高可见光透射率的建筑用及住宅用玻璃窗或玻璃幕墙。因此，在镀覆了“隐避”窗用玻璃板之后，需要溅射镀膜机继续工作以完成建筑及住宅用镀膜玻璃的订货时，必须关闭镀膜机才能形成新的镀层体系。如果能避免这种关闭，就能获得显著的经济效益。再次发现缺少可匹配性。
美国专利5,344,718公开了某些对建筑及住宅用途有极好适用性的独特的溅射镀膜层体系，这是因为该体系不仅达到了良好的化学和机械耐久性，而且有良好的日光控制性。通常认为这种体系是“低-E”玻璃(镀层)，因为其半球辐射率(Eh)一般小于约0.16，而其标准辐射率(En)一般小于约0.12。以另一种方式测量，其薄膜电阻优选小于约10.5欧姆/平方。此外，对于标准玻璃厚度(例如2mm-6mm)而言，可见光透射率优选约为78％或更高(与上述可热处理的“隐避”窗镀层体系的某些优选实施方案中小于约22-23％的透射率相比)。
US5,344,718专利中的这项发明通过采用了一种镀层体系而达到了极好的低-E性、高可见光透射率值、以及良好的化学耐久性和耐磨性，所述镀层体系一般包括(由玻璃向外)：Si3N4底层、第一镍或镍合金层、银层、第二镍或镍合金层、和Si3N4面层。在某些优选实施方案中，镀层体系由玻璃向外基本上包括：Si3N4/Ni∶Cr/Ag/Ni∶Cr/Ag/Ni∶Cr/Si3N4。该七层体系比上述五层体系显示出稍高的耐久性和耐磨性。然而在每种体系中，优选的Ni∶Cr层是镍铬合金，即Ni∶Cr的重量比为80/20，而且其中大部分铬是Cr的氮化物，因为该Ni∶Cr层是在含氮气氛中形成的。
遗憾的是，这种耐久、低-E、高可见光透射率的玻璃镀层体系被证明是不可热处理并且不匹配的。现已证实其原因不是银层的任何氧化作用，而是由于在热处理过程中，金属银层因为不湿润而变得不连续，这种情况是由于在热处理过程中，Ni∶Cr包覆层不足以使银层保持连续。因此，这些在其它方面有益的镀层体系不能用于需接着进行热处理(如通过回火、热强化和弯曲)的镀膜玻璃上。遗憾的是，为了达到所希望的低-E值，必须使用银层。
应当记得，在这方面，可热处理的溅射镀膜镀层体系的用途不仅在于汽车防风领域。如上所述，某些建筑及住宅.用途也需要使镀膜玻璃再经回火、弯曲、或热强化。更进一步讲，即使上述US5,344,718专利的低-E玻璃体系是可热处理的(实际上不能)，一般也不能将可见光透射率值调节到足以制成“隐避”窗的低值。
美国专利5,376,455以开了某些可热处理的、“低-E”镀层体系。这些体系一般包括(从玻璃向外)：第一Si3N4层(约350-450)、第一镍或镍铬合金层(约20)、银层(约50-120)、第二镍或镍合金层(约7)和第二Si3N4层(约450-550)。尽管达到了热处理体系及未热处理体系之间的匹配性，但仅限于达到两种不同镀层体系(例如Col.23，1.68-Col.24，1.21)的匹配。因此，虽然这种体系在该领域中有显著进步，但一般不能提供一种镀层体系，该体系是“可热处理”的，而且至少具有一种被认为在热处理之后与热处理之前的其自身(例如同时镀覆到同一批基体上、或稍后镀覆到其它批基体上的同一种镀层体系)相匹配的足够低的玻璃一侧反射率ΔE。
正如可从上面看到的，迄今为止，如果熟练技术人员希望继续通过采用Si3N4层而达到已知的有益耐磨性和防腐性(即耐化学性)，并希望避免停机时间的浪费或为达到匹配性而不得不生产不同镀层体系，与此同时达到可热处理性并且还在合理的宽范围内对于改变日光控制性具有适应性，从而避免另外的生产停工(满足不同用户的需求)，那么该技术人员面临着一种尚未解决的问题。
显然该领域需要一种既具有溅射镀层的优点同时又克服了该领域的上述问题和缺点的溅射镀膜镀层体系。本发明的目的就是满足该领域的这一需求以及其它的在公开了下述内容之后对于熟练技术人员而言变得显然的需求。
一般说来，本发明通过提供一种玻璃制品而满足了该领域的上述需求，该玻璃制品包括带有溅射镀膜镀层体系的玻璃基体，所述镀层体系由玻璃基体向外包括(a)氮化硅(Si3N4)底层，(b)含有镍或镍合金且基本不含任何氮化物的基本上为金属的层，和(c)氮化硅(Si3N4)面层，其中每一层都具有足够的厚度，因此当玻璃基体的厚度约为1.5mm-13mm并且其上具有上述镀层体系时，具有这种镀层的玻璃制品在热处理时与具有同样镀层体系的玻璃制品是匹配的，表现在用Hunter法测得的玻璃一侧反射率ΔE(即ΔEH，ASTM2244-93)不超过约2.0。在另一优选实施方案中，具有这种镀层的玻璃制品也是可热处理的，并且其可见光透射率约为1-80％，更优选低于约70％。在其它一些优选实施方案中，热处理前及热处理后的玻璃制品都是耐久的和耐化学性的。在本发明更进一步优选的实施方案中，镀层体系不含任何银层。
本发明进一步通过提供一种镀膜玻璃制品的热处理方法而满足了该领域的上述需求，所述方法一般包括：
a)向玻璃基体上溅射镀覆一镀层体系，该体系包括(由玻璃基体向外)：氮化硅底层、含有镍或镍合金的基本上为金属的层、和氮化硅面层，以及
b)接着将这种镀膜的玻璃基体进行热处理，所述热处理选自弯曲、回火、热强化及它们的结合，以及
c)与热处理前的这种镀膜的玻璃基体相比，经热处理后，所得制品的玻璃一侧反射率ΔEH(定义如上)不超过约2.0。
上述镀层体系优选通过将所需厚度的每一镀层溅射镀覆到玻璃基体上而形成。尽管玻璃的厚度可以有很大变化，但一般玻璃制品都属于浮法玻璃类，而且其厚度约为1.5-13.0mm(即约0.060″-0.50″)，更经常性地约为2mm-6mm。所述的玻璃可以是着色或不着色玻璃或是花纹玻璃。这种玻璃可以是单强度型的。
为了适当地定义本发明所达到的可匹配性，这里测量了洁净玻璃基体的各种前面指定的性能(以此强调可匹配性是由镀层体系达到的而不是靠基体的作用)。本发明的独特的镀层体系所达到的典型性能如下：
    性能     范围 优选范围
可见光透射率  (TY) 约1-80％ ＜约70％
可见光反射率(玻璃一侧)   (RGY) 约4-55％ 约5-45％
可见光反射率(镀膜一侧)   (RfY) 约4-65％ 约5-45％
可见色(玻璃一侧) 银、白镴、蓝、灰 约ah，O±2bh，-4±4
辐射率(标准辐射率即En和半球辐射率Eh) 约0.10-0.75 约0.2-0.75
薄膜电阻     (RS) 约20-500欧姆/平方 约20-300欧姆/平方
日光透射率   (Ts) 约1-80％ ＜约70％
玻璃一侧的反射率ΔEH 约≤2.0 ＜约1.5
镀膜一侧的反射率ΔEH 约≤5.0 ＜约4.0
可见光透射率ΔEH ≤5.0 ≤4.0
在最优选的本发明的构成中，无论在热处理之前还是之后，所得制品及其镀层体系都显示出优异的耐化学性和耐久性(即耐磨性或耐划伤性)。
图1是玻璃基体上镀层体系的部分侧剖图，说明了本发明的一种实施方案。
某些术语是通用于玻璃镀膜领域的，尤其当定义建筑和/或汽车领域用镀膜玻璃的特性和日光控制性时。这里根据公知的含义而使用这些术语。例如以下所用的：
可见波长光强度，“反射率”用其百分数定义并记为RXY(即在ASTM 308-85中提及的Y值)，其中“X”是表示玻璃一侧的“G”，或是表示镀膜一侧的“F”。“玻璃一侧”(即“G”)是指从与存在镀层的玻璃基体一侧相对的一侧来观察，而“镀膜一侧”(即“F”)是指从存在镀层的玻璃基体一侧来观察。
颜色性能用“a”坐标和“b”坐标测量。这些坐标注有下标“h”以表明采用惯用的Hunter法(或单位)Ill.c，10°观测仪，依据ASTMD-2244-93“根据仪器测量的色坐标计算色差的标准测试方法”9/15/93，正如ASTM E-308-85，ASTM标准年报06.01卷“利用CIE体系计算物体颜色的标准方法”所增加的。
术语“辐射率”和“透射率”是该领域公知的，这里使用其公知的含义。因此，例如在这里术语“透射率”指日光透射率，由可见光透射率(TY)、红外光能透射率、和紫外光透射率构成。总太阳能透射率(TS)通常表征为这些其它值的加权平均数。就这些透射率而言，这里提到的可见光透射率是在380-720nm处用标准I lluminant C(CIE国际照明委员会指定标准照明体C)方法所表征的透射率；红外光透射率为800-2100nm处的透射率；紫外光透射率为300-400nm处的透射率；总日光透射率为300-2100nm处的透射率。然而对于辐射率来说，采用的是特殊的红外范围(即2,500-40,000nm)，正如以下所述。
可采用已知的常规方法测量可见光透射率。例如用光谱光度计如Beckman5240(Beckman Sci.Inst.Corp.)得到透射光谱曲线。然后用上述ASTM 308/2244-93分类法计算可见光的透射率。如需要，采用的波长测试点的数量可以比规定的少。另一种测量可见光透射率的方法采用了分光计如可从市场购得的由太平洋科学公司制造的Spectragard光谱光度计。该装置直接测量并记录可见光透射率。这里记录及测量的可见光透射率(即CIE三色值中的Y值，ASTM E 308-85)采用了Ill.C.，10°观测仪。
“辐射率”(E)是对给定波长的光的吸收和反射性能或其量度。通常用下式表示：E＝1-反射率镀膜。
从建筑的观点上看，辐射率值在所说的“中程”、有时也称为红外光谱的“远程”、即约2,500-40,000nm内变得非常重要，例如由L awrence Berkeley研究所的WINDOW 4.1程序，LBL-35298(1994)规定的，以下论及。这里所用的术语“辐射率”是指在该红外区内测得的辐射率值。如由1991年提出的通过测量红外能而计算辐射强度的ASTM标准规定的，该标准由主要的玻璃制造者协会提出，名为“用辐射计测量法测量并计算建筑用平板玻璃制品的辐射强度的测试方法”。该标准及其规定结合入本文供参考。该标准中，辐射率记作半球辐射率(Eh)和标准辐射率(En)。
对这种辐射率值测量结果数据的实际累加是常用的，并可通过采用如带有“VW”附件的Beckman型4260光谱光度计(Beckman Scientific Inst.公司)而进行。该光谱光度计测量作为波长函数的反射率，由此根据上述1991年提出的ASTM标准计算出辐射率，所述标准已引入本文供参考。
这里使用的另一术语是“薄膜电阻”。薄膜电阻(Rs)是该领域公知的术语，这时使用其公知的含义。一般说来，该术语是指任意平方的玻璃基体上的镀层体系对通过该镀层体系的电流的电阻，以欧姆计。薄膜电阻表征了镀膜反射红外能的好坏，因此薄膜电阻经常与辐射率一起被用来作为这一性能的量度。“薄膜电阻”可用4点探针欧姆表方便地测量，该欧姆表例如具有磁控管仪器公司探头的可分配的4点电阻率探测仪，M-800型(由SignatoneCorp.of Santa Clara(California)生产)。
这里所用的“化学耐久性”或“化学耐久的”与该领域的术语“耐化学性”或化“学稳定性”是同义的。通过将一块2″×5″的镀膜的玻璃基片样品在约500cc 5％HCl中煮沸1小时(即在约220°F)而测定化学耐久性。如果经这种1小时的煮沸之后，样品的镀层体系没有出现直径大于约0.003″的针孔，则认为该样品通过了这一测试(因此该镀层体系是“耐化学性的”或认为其具有“化学耐久性”)。
这里所用的“机械耐久性”或简称为“耐久的”是由两项测试中的一项所定义的。第一项测试采用太平洋科学磨损试验机(或等效装置)，其中，一个2″×4″×1″的尼龙刷以150gm重量循环经过镀层体系500个循环，所述镀层体系镀覆在一块6″×17″的样品上。另一项可作为替换的测试中，采用常规的泰伯尔耐磨试验仪使一块4″×4″的样品经受两个C.S.10F磨耗轮的300次循环，每个轮上加有500gm重量。在每一项测试中，如果在可见光下用眼观察不到显著的、令人注意的划痕，则认为通过了该项测试，并将该制品称为“耐久的”。
所述镀层体系中各种镀层的厚度用下述可替换的方法测量，因此这里所用的术语“厚度”是由下述可替换的方法定义的。一种方法采用了已知的光学曲线，另一种方法采用了常规的指针椭圆光度计(即轮廓曲线测定仪)。在另一个特别有益的方法中，采用了“n&k”分析仪(n&k Technology，Inc.，Santa Clara，Calif.)。认为该方法一般性地公开于美国专利4,905,170中，与此同时还公开了测定被测镀膜的“n”值(即折射率)和“k”值(即消光系数)的技能。将该专利公开的内容结合入本文以供参考。除了注意这里所记录及使用的厚度单位记为埃()之外，这类步骤及方法是该领域熟练技术人员所公知的，因此无需进一步说明。
这里所用的另一个对于理解发明主题十分重要的术语是“ΔE”。该术语是该领域公知的，与此同时在前述ASTM-2244-93(其公开内容引入本文供参考)中记载了各种测ΔE的方法。
根据ASTM-2244-93的记载及测定，“ΔE”适用于表示制品在反射率和/或透射率方面的改变(或其减少)  (以及因此而产生的颜色外观改变)。其中记载的ΔE用“ab”法、Hunter(H)法、和/或Friele-MacAdam-Chickering(FMC-2)法测定。对于本发明来说，所有这些方法都认为是有用且等效的。然而为了方便起见，这里所用的以及本发明权利要求中所述的“ΔE”是用Hunter法测定的，因此一般表示为ΔEH。所以，例如，当叙述镀覆基体的“玻璃一侧的反射率ΔEH”不超过约2.0时(如本发明所期望的)，该2.0值为Hunter值。当然，在本发明的范围内，该值等效(相应)于用ASTM-2244-93中记载的另两种方法(“ab”法或FMC-2法)之一测定的值或是任何其它用于计算这种改变或其减少的方法测定的值。
在这方面，应当指出，从商业目的所期望的，为达到可匹配性，玻璃一侧的反射率性能必须具有尽可能低的ΔE，而且对于大多数但并非全部的应用而言，镀膜一侧的反射率和/或透射率的ΔE是不重要或是重要性显著小的。尽管如此，当后两种ΔE值得考虑时，为达到可匹配性，本发明期望的“镀膜一侧的反射率ΔE”以及“可见光透射率ΔEH”应当小于或等于约5.0，优选小于或等于约4.0。当然这些值是Hunter值以及以上论及的关于用其它方法测定的等效性的值。
现转到图1，该图说明的是本发明典型实施方案制品的部分剖视图。其中玻璃基体1上镀有Si3N4底层2(即镀层1)、非氮化的镍或镍合金(优选80/20镍铬合金)中间层3(即镀层2)、以及Si3N4面层4(即镀层3)。镀层自身分别指镀层1、2、3。
用于在玻璃基体1上形成各种镀层的方法和装置可以是常规的多室(多靶)溅射镀覆系统，如Airco，Inc.制造的。可用于此的镀覆机的例子是G-49 Airco Inc.大面积平板玻璃溅射镀膜机。这里应当注意到，通过使用常规溅射镀覆工艺而无需用特殊方法以降低内应力从而达到独特的结果是本发明的一个方面，所述的降低内应力的特殊方法记载于上述美国专利5,377,045中。
如图1所示，该实施方案中仅采用了三层镀层，即镀层1、2、和3。用上述“n&K”方法测得的该特定实施方案中由玻璃向外的各镀层一般厚度范围及优选厚度范围是：
镀层 成分 厚度() 优选厚度()
   123  Si3N4 *Ni或镍铬合金**Si3N4 * 约5-70约30-150约200-500 约30-50约50-100约300-400
*靶可以混有至多约6％(重量)的铝和/或不锈钢(如SS#316)，以大约这种含量出现在形成的镀层中。**优选采用镍铬合金(例如80/20的Ni/Cr重量比)。
本发明的一个特点是当镍合金(或纯镍)与以上陈述的Si3N4镀层一起使用时，迄今仍认为的必须采用高含量的镍合金(或纯镍)以达到可热处理性这样一个基本限制不再适用了。尽管镀层2应当是含镍镀层，但无需是高镍含量合金。然而对于本发明来说，尽管在含镍镀层中允许有极少量或少量氧化，但要求含镍镀层必须保持基本上不含任何氮化物以便具有足够的耐化学性，以满足大多数需要。但是对于获得最佳匹配性而言，已发现基本上不允许出现镍或镍合金的氧化是优选的。在这方面，尽管大多数情况下氮化物不会显著地影响获得可热处理性，但发现形成这种氮化物会降低化学耐久性，该化学耐久性是用前述5％HCl煮沸试验测量的。
如上所述，含镍镀层可以基本上是纯镍的，但更优选为简单Ni/Cr合金。一种可用的这类合金的例子是相当大量的镍含量低至约10％(重量)的不锈钢(例如SS-316，其10％是Ni，90％是其它，主要为Fe和Cr)。当然，高含量镍/铬合金仍优选用于本发明。这包括80/20(重量)的Ni/Cr和Haynes214合金，其标准组成以重量计基本构成如下：
元素            wt.％(近似)
Ni              75.45
Fe              4.00
Cr              16.00
C               0.04
Al              4.50
Y               0.01其它可用于本发明的实际应用中的Ni/Cr合金的例子包括因康镍合金(Inconel)和镍铬合金。一般说来，本发明所期望与Si3N4夹层一起使用的金属层包括至少约10％(重量)的镍，而且这些金属层必须以基本上未氧化的形式(或仅经过少量氧化)而存在，并优选基本上无氮化物，从而达到最高的化学稳定性。
尽管图中表现的是一种三镀层体系，但应当了解到本发明不限定于此。如需要可以增加其它镀层以达到其它的目的和性能。然而这类其它镀层不应当对本发明特有的可匹配性产生相反的影响。因此这里所用的术语“基本上由……组成”是指本发明不限于三镀层体系，尽管在上述基本的三层镀层上添加一或多层镀层，只要仍达到可匹配性即可。
                 实施例
以下镀层体系是用前述G-49 Airco大面积平板玻璃溅射镀覆机溅射镀覆到厚1/4″、宽100″、长144″的洁净玻璃基体上的，使用的是掺了约6％(重量)铝的Si靶并采用指出的常规溅射镀覆方法。采用了上述化学及耐久性试验。所用热处理的例子是一种典型的回火方法，该方法使用工业用回火炉，使样品在约1265°F(685℃)经历一个大约3分钟的周期(实际样品温度约1200°F)，并骤冷至室温。回火前样品被切割成24″×36″的片。根据上述“n&k”方法测量镀层厚度。实施例1(参照图中的标号)
采用上述常规镀覆机和以下列出的镀覆机参数，将第一底层2[镀层1]镀覆到上述洁净浮法玻璃基体上，镀覆约40厚。然后镀覆约75A厚的镍铬合金(80/20的Ni∶Cr重量比)中间层3[即镀层2]。最后镀覆约350厚的Si3N4面层[镀层3]。
如此形成的镀覆样品在回火前及回火后都通过了上述机械耐久性和耐化学性测试，并且属于以上定义的可热处理的。以下记录了其日光控制性和HunterΔE值(以及Hunter色坐标ah和bh)。简单地说，发现该镀膜制品是耐久、可回火、可弯曲的，并且经回火热处理后其外观没有明显的变化。因此以商业上允许为基准认为所述镀膜制品是可匹配的，并且具有适用于单片或IG多片建筑用玻璃制品的满意的高日光控制性。镀覆机参数
镀层 材料 N2％ Ar％   压力(乇)  阴极功率 阴极电压  阴极电流 线速度 通过次数
  1 硅 80  20  2.0×10-3  27.7kW 414V  66.9A  334   1
  2 镍铬合金 0 100  2.0×10-3  18.1kW 429V  42.1A  334   1
  3 硅 80  20  2.0×10-3  334.9kW 462V  724.9A  334   1
光学性能(Ill.C，10°观察仪，Hunter值)
       性能     Y      ah      bh
玻璃一侧反射率(未经热处理)     12.93     -1.1     -8.1
玻璃一侧反射率(经热处理)     12.75     -1.2     -7.75
        ΔE     0.44
镀膜一侧反射率(未经热处理)     9.79     1.53     4.05
镀膜一侧反射率(经热处理)     10.67     1.15     3.34
        ΔE     1.6
透射率(未经热处理)     51.85     -2     -2.59
透射率(未经热处理)     52.99     -1.93     -2.29
        ΔE     0.84
热处理前，标准辐射率(En)和半球辐射率(Eh)分别为0.73和0.69，薄膜电阻(Rs)为269欧姆/平方。热处理后，En和Eh分别为0.71和0.67，Rs为235欧姆/平方(即在前述“可热处理”的定义之下，认为每种情况都没有显著变化)。实施例2
重复以上实施例1的步骤，只是将镍铬合金中间层3[即镀层2]的厚度增加至约140(即约为实施例1中的2倍)，从而基本上将可见光透射率降低到真正的“隐避”窗范围(即玻璃一侧的可见光透射率约为30％)。下表分别列出了镀覆机参数及性能。以商业上允许为基准再次发现该镀膜制品是可匹配的、耐久的、可回火的、可弯曲的，并且经热处理后其外观未表现出明显的改变。也显示出所希望的日光控制性，尤其是在为了隐避而需要低可见光透射率之场合。镀覆机参数
镀层 材料 N2％ Ar％   压力(乇) 阴极功率 阴极电压 阴极电流 线速度 通过次数
  1 硅 80 20 2.0×10-3 28.2kW 414V 68.1A 334 1
  2 镍铬合金 0 100 2.0×10-3 39 3kW 454V 86.6A 334 1
  3 硅 80 20 2.0×10-3 334.9kW 462V 724.9A 334 1
光学性质(Ill.C，10°观察仪，Hunter值)
        性能     Y     ah      bh
玻璃一侧反射率(未经热处理)    20.6    0.9    -3.59
玻璃一侧反射率(经热处理)    19.5    -1.22    -5.03
    ΔE    1.9
镀膜一侧反射率(未经热处理)    15.6    2.45    14.31
镀膜一侧反射率(经热处理)    16.4    1.47    10.43
    ΔE    3.9
透射率(未经热处理)    32.1    -1.8    -5.93
透射率(未经热处理)    33.4    -1.55    -3.82
    ΔE    2.5
热处理前，标准辐射率(En)和半球辐射率(Eh)分别为0.55和0.54，薄膜电阻(Rs)为108欧姆/平方。热处理后，En和Eh分别为0.48和0.49，Rs为89欧姆/平方(在前述“可热处理”的定义之内，再次认为每种情况都没有显著变化)。
一旦给出了以上公开内容，则一些其它的特点、改进和提高对于该领域熟练技术人员而言变得显而易见了。因此认为这种其它的特点、改进和提高属于本发明的一部分，本发明的范围由以下权利要求确定。

Claims (21)

1、一种玻璃制品，包括玻璃基体，该基体上带有溅射镀覆的镀层体系，该镀层体系由玻璃基体向外包括：
a)由氮化硅构成的底层；
b)含有镍或镍合金的基本上为金属的层；以及
c)由氮化硅构成的面层；
其中所述的镀层都具有足够的厚度，因而当光厚度约为1.5mm-13mm的玻璃基体上具有上述镀层体系时，则如此镀层的玻璃制品在热处理后其玻璃一侧的反射率ΔEH不超过约2.0。
2、一种权利要求1的玻璃制品，其中所述镀层体系基本上无银。
3、一种权利要求1的玻璃制品，其中镀层(a)的厚度约为5-70，镀层(b)的厚度约为30-150，镀层(C)的厚度约为200-500。
4、一种权利要求3的玻璃制品，其中所述的如此镀层的玻璃制品在热处理后其镀膜一侧的反射率ΔEH不超过约5.0，其可见光透射率ΔEH不超过约5.0，并且在热处理前后都具有以下性能：
TY           约1％-80％
RGY         约4％-55％
RfY         约4％-65％
En           约0.1-0.75
Eh           约0.1-0.75
Rs           约20-500欧姆/平方。
5、一种权利要求3的玻璃制品，其中镀层(a)的厚度约为30-50，镀层(b)的厚度约为50-100，镀层(c)的厚度约为300-400，其中所述玻璃制品在热处理前后都具有以下性能：
TY       小于约70％
RGY     约5％-45％
RfY     约5％-45％
可见色    ah  约0±2
          bh  约-4±4
En        约0.2-0.75
Eh        约0.2-0.75
Rs        约20-300欧姆/平方。
6、一种权利要求5的玻璃制品，其中所述制品是耐久并耐化学性的，而且镀层(b)基本上无任何氮化物。
7、一种权利要求5的玻璃制品，其中所述的热处理是回火，而且镀层(b)基本上无任何氧化物。
8、一种权利要求1的玻璃制品，其中镀层(a)的厚度约为40；镀层(b)的厚度约为75，且镀层(b)基本上由不氮化和不氧化的镍铬重量比为80∶20的镍铬合金构成；镀层(c)的厚度约为350，而且其中所述的玻璃制品在回火前后都具有以下性能：
TY           约50％
RGY         约13％
RfY         约10％-11％
玻璃一侧的反射率ΔEH小于约1.5，
镀膜一侧的反射率ΔEH小于约4.0，
可见光透射率    ΔEH小于约4.0。
9、一种权利要求8的玻璃制品，其中：
所述玻璃一侧的反射率ΔEH小于约0.5，
所述镀膜一侧的反射率ΔEH小于约2.0，
所述可见光透射率    ΔEH小于约1.0，而且其中所述玻璃制品是耐久的且耐化学性的。
10、一种权利要求1的玻璃制品，其中：
镀层(a)的厚度约为40，
镀层(b)的厚度约为140，且由基本上不氮化和不氧化的镍铬重量比约为80∶20的镍铬合金构成，
镀层(c)的厚度约为350，且其中所述的玻璃制品在回火前后都具有以下性能：
TY          约30％
RGY        约20-21％
RfY        约16％其玻璃一侧反射率ΔEH小于约2.0，镀膜一侧反射率ΔEH小于约4.0，可见光透射率小于约3.0，而且其中所述的玻璃制品是耐久的并耐化学性的。
11、一种权利要求5、8和10的玻璃制品，其中所述的氮化硅镀层含有至多约6％(重量)的铝，所述镀层体系基本上无银，并基本上由所述镀层(a)、(b)、和(c)构成，且所述镀层体系是耐久的并耐化学性的。
12、一种对镀膜玻璃制品进行热处理的方法，包括：
a)将权利要求1的镀层体系溅射镀覆到玻璃基体上，以及
b)其后将上述镀覆的玻璃基体进行热处理，该热处理选自弯曲、回火、热强化及其结合；
其中在上述热处理后，所得制品的玻璃一侧反射率ΔEH不超过约2.0。
13、一种权利要求12的对镀膜玻璃制品进行热处理的方法，其中所述的热处理基本上由将所述玻璃回火所构成：使所述玻璃制品处于高于约1200°F的环境温度下并聚冷一段时间从而使所述玻璃制品回火。
14、一种对镀膜玻璃制品进行热处理的方法，包括：
a)将权利要求3的镀层体系溅射镀覆到玻璃基体上，以及
b)其后将上述镀覆的玻璃基体进行热处理，该热处理选自弯曲、回火、热强化及其结合；
其中在上述热处理之后，所述玻璃制品其玻璃一侧的反射率ΔEH不超过约2.0，镀膜一侧的反射率ΔEH不超过约5.0，且在热处理前后都具有以下性能：
TY      约1％-80％
RGY    约4％-55％
RfY    约4％-65％
En      约0.1-0.75
Eh      约0.1-0.75
Rs      约20-500欧姆/平方。
15、一种权利要求14的对镀膜玻璃制品进行热处理的方法，其中所述溅射镀覆包括镀覆约30-50厚的镀层(a)，镀覆约50-100厚的镀层(b)，和镀覆约300-400厚的镀层(c)，以及
其中所述的玻璃制品在热处理前后都具有以下性能：
TY         小于约70％
RGY       约5％-45％
RfY       约5％-45％
可见色     ah    约0±2
           bh    约-4±4
En        约0.2-0.75
Eh        约0.2-0.75
Rs         约20-300欧姆/平方，而且其中所述的玻璃制品在热处理前后都是耐久的和耐化学性的。
16.一种权利要求15的方法，其中所述镀层(b)的镀覆厚度约为75，而且该玻璃制品在热处理前后其TY约为50％，可见光透射率ΔEH小于约1.0，玻璃一侧反射率ΔEH小于约0.5。
17、一种权利要求15的方法，其中所述镀层(b)的镀覆厚度约为140，而且该玻璃制品在热处理前后其TY约为30％，可见光透射率ΔEH小于约3.0。
18、一种制备热处理的溅射镀膜玻璃制品的方法，该制品从美学角度讲与未经热处理的溅射镀膜玻璃制品是可匹配的，因而至少具有基本相同的玻璃一侧外观，该制备步骤包括：
a)向至少两个玻璃基体的每一个上溅射镀覆权利要求1的镀层体系，
b)将上述溅射镀覆基体的至少一个进行热处理，所述热处理选自弯曲、回火、热强化及其结合；由此，上述的至少一个基体在热处理后与上述未热处理的基体相比，玻璃一侧的反射率ΔEH不超过约2.0，
如此形成的上述热处理的溅射镀覆基体具有与上述未热处理的溅射镀覆基体基本相同的玻璃一侧外观。
19、一种权利要求18的方法，其中所述玻璃基体在热处理前后都具有以下性能：
TY         小于约70％
RGY       约5％-45％
RfY       约5％-45％
可见色     ah   约0±2
           bh   约-4±4
En        约0.2-0.75
Eh         约0.2-0.75
Rs         约20-300欧姆/平方，而且其中与所述的未热处理基体相比，所述的热处理基体在热处理后具有以下性能：
镀膜一侧反射率ΔEH不超过约5.0，
可见光透射率ΔEH不超过约5.0。
20、一种权利要求18的方法，其中所述玻璃基体在热处理前后都具有以下性能：
TY        约50％
RGY      约13％
RfY      约10-11％
玻璃一侧反射率ΔEH小于约1.5；
镀膜一侧反射率ΔEH小于约4.0；
可见光透射率ΔEH小于约4.0；而且其中所述的镀覆的玻璃基本是耐久的和耐化学性的。
21、一种权利要求18的方法，其中所述玻璃基体在热处理前后都具有以下性能：
TY        约30％
RGY      约20-21％
RfY      约16％
玻璃一侧反射率ΔEH小于约2.0；
镀膜一侧反射率ΔEH小于约4.0；
可见光透射率ΔEH小于约3.0；而且其中所述的镀覆的玻璃基体是耐久的和耐化学性的。
CN96121374A 1995-12-14 1996-12-14 匹配的、可热处理的、耐久的、不反射的溅射镀膜玻璃及其制造方法 Pending CN1157806A (zh)

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