CN1435507A - 耐蚀、耐磨装饰涂层 - Google Patents

耐蚀、耐磨装饰涂层 Download PDF

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CN1435507A
CN1435507A CN03106485A CN03106485A CN1435507A CN 1435507 A CN1435507 A CN 1435507A CN 03106485 A CN03106485 A CN 03106485A CN 03106485 A CN03106485 A CN 03106485A CN 1435507 A CN1435507 A CN 1435507A
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component
goods
transition layer
containing metal
corrosion
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J·G·希克
J·格雷姆伯茨
I·宋
T·J·奥柏林
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Moen Inc
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Abstract

一种新的加工制品，如水龙头或其它五金制品，其具有一种特定的装饰色，而且耐腐蚀、耐磨损和耐化学侵蚀。制品包括一个基体，一个或多个涂覆于基体上的耐腐蚀层，具有从第一组分到第二组分系统变化的组分的薄过渡层，其中的第一组分，至少部分有防腐蚀作用，其中的第二组分决定可见色或过渡层涂覆的基体部分。

Description

耐蚀、耐磨装饰涂层
技术领域
本发明涉及用于加工制品的装饰涂层，比如水龙头和包括喷淋头、孔罩、澡盆喷嘴等在内的相关管道产品。更具体地说，本发明涉及这种产品的耐蚀、耐磨、抗化学侵蚀的装饰涂层。本发明特别涉及这种装饰涂层的耐蚀性能，这是目前装饰涂层普遍存在的问题。很多现有技术专利公开了使用锆以提供耐蚀性黄铜色表面的装饰涂层。最近，已经证明采用物理气相沉积(PVD)工艺且金属种类中只含锆和铪的装饰涂层，与含其它金属的装饰涂层相比，是少见的而且具有一定的优点，因为通常它们不会降低涂覆制品的耐蚀性能。这种涂层可以用来扩大装饰PVD颜色的范围，可以从单一的黄铜色色调扩展到黑色、灰色和金色色调。也是在最近，已经证实作为唯一的金属种类存在于表面装饰涂层的锆和铪并不是保证涂覆制品耐蚀性能不降低的充分条件。一些非黄铜色的装饰PVD颜色，特别是铜色色调范围，即使在表面的PVD涂层中只含有锆金属，在腐蚀测试中的结果仍然不尽人意。本发明颜色范围可扩展到包括铜色。更一般地，本发明能用来解决当物料层需要同时完成多个功能时的表面工程中遇到的相互矛盾的常见问题，所以对它的厚度要进行若干不同且相互矛盾的限制。
发明概述
本发明涉及具有装饰涂层的加工制品，更具体地说涉及具有耐蚀、耐磨、抗化学侵蚀性能的涂层。本发明的主要目的是提供一种新的加工制品，它具有特定的装饰色，例如铜色，而且包括一层薄薄的外部过渡层，其中组成从第一组分到第二组分系统地变化。
另外一个目的是所述种类的加工制品，其中外部过渡层和其下面的颜色层是通过物理气相沉积的，根据特定的沉积工艺参数，能提供不同的颜色。
另外一个目的是所述种类的耐蚀加工制品，例如门上的五金制品或水龙头或具有强防腐性能的相关管道元件。
本发明的另一个目的是提供具有外部过渡层的耐蚀加工制品，过渡层由第一组分和第二组分组成，其中第一组分至少部分具有防腐蚀的功能，并且其中第二层组分决定制品的可见色。
在随后的说明书、附图和权利要求中可以明显看出其它目的。
附图详述
本发明在下图中进行图解说明，其中：
图1是本文公开的加工制品局部；
图2是在不同的材料深度上沉积的过渡层和颜色层组分的图表；
图3类似于图2，是涂层在空气中暴露后的图表；
图4是依据表1加工的制品的XPS分析结果的图表。
优选具体实施方式的描述
许多家居物件，例如水龙头和相关的管道产品，包括设计使其同时具有装饰和使用功能的元件。经常地，这些元件首先由一个成形和具有机械性能的基体组成，其次由一个用来为制品提供装饰性外观、具有防腐蚀或防玷污性能、防化学侵蚀性能、防磨损或冲击性能，或这些增强性能的结合的表面涂层(finish)组成。通常，表面涂层(finish)由一组一层或多层比基体尺寸薄的材料组成。表面涂层的加工一般由涂覆涂层的必要步骤和加入其它包括清理表层或通过物理或化学方法改变表层结构或化学性能的中间步骤组成。
直到大约20世纪80年代，发展最好的装饰涂装工艺为用液体或粉末聚合物系统进行电镀和喷漆。最近出现了新的涂装工艺种类，其依据的新技术通常涉及采用真空室或压力管。一系列的此类现代化工艺包括PVD、CVD、PECVD、离子喷漆和MOCVD。物体气体沉积(PVD)是一类工艺的集合名称，其在20世纪90年代，在美国特别流行，用于将耐用、耐划、抛光黄铜表面涂层涂覆于Zn、塑料、钢或黄铜基体上。本申请的受让人，Moen Incorporated的美国专利5,759,677描述了这样一种工艺，其将黄铜色表面耐用的涂层涂覆于基体上，如水龙头。宾夕法尼亚，Baldwin Hardware Corp.of Reading的美国专利5,814,415、5,783,313、5,716,721、5,693,427、5,667,904、5,654,1085,648,179、5,641,579、5,639,564、5,626,972、5,552,233、5,484,663、5,482,788、5,478,660、5,478,659、5,476,724和5,413,874描述了一系列工艺，主要着重于防腐和为不同种类的五金制品提供黄铜表面装饰涂层，在此将上述专利中提到的和此类工艺中采用的特定参数引入本发明作为参考，因为它们可以为本领域技术人员提供关于使用PVD工艺的技术。
上述专利描述了Zr与N和C结合形成的化合物的应用，以形成PVD抛光的黄铜色表面涂层。一般的PVD涂层涂有颜色，并具有防划和耐化学侵蚀性能。在金属基体上，通常在PVD层或防腐蚀层下装有单独的电镀层系统。电镀系统通常由一个标准的Cr电镀系统组成，有时有一些较贵的替代品如Ni、两相Ni、钯镍、锡镍或镍硼和钨，具体细节在上述的Baldwin Hardware专利中已经公开。PVD ZrN抛光黄铜只是能够用一种或多种金属并采用PVD工艺产生一大系列颜色涂层中的一种，工艺中采用的气体包括氮气、碳、氢气、氩气和氧气。
事实上ZrN表面涂层是不常见的，因为当它应用于对腐蚀敏感的基体，如Zn，并采用Cr电镀防腐系统时，可以提供可接受的防腐性能。也已经证实，在涂装的装饰涂层中采用的其它金属如Ti、Al或Cr确实会降低整个涂层的防腐性能。最近，已经证明采用PVD工艺且金属种类中只含锆和铪的装饰涂层，与含其它金属的装饰涂层相比，是少见的而且具有一定的优点，因为通常它们不会降低涂覆制品的耐蚀性能。这种涂层可以用来扩大装饰PVD颜色的范围，可以从单一的黄铜色调扩展到黑色、灰色和金色色调。参见美国专利6,245,435，其公开的内容在此引入并作为参考。
也是在最近，已经证实作为唯一的金属种类存在于表面装饰涂层的锆和铪并不是保证在某种颜色条件下涂覆制品的耐蚀性能不降低的充分条件。一些非黄铜色的装饰PVD颜色，特别是铜色色调范围，即使在表面的PVD涂层中只含有锆金属，在腐蚀测试中的结果仍然不尽人意。本发明颜色范围可扩展到包括铜色。更一般地，本发明能用来解决当物料层需要同时完成多个功能时的表面工程中遇到的相互矛盾的常见问题，所以对它的厚度要进行若干不同且相互矛盾的限制。
图1为根据本发明公开内容的加工制品的部分截面图。所加工的基体或制品如10所标示，优选为表面基本无缺陷和孔洞的物质，优选选自Zn、Al和塑料。
直接与基体10相接的是防腐蚀层12，它可为一层或多层的Cu、Ni和Cr。这些防腐蚀层在本技术领域是公知的，这样的层也可为一层或多层。可选择地，防腐蚀层可以选自Ni、两相Ni、Ni/Pd；Ni、W和B；或Ni和Sn。所有这些防腐蚀层已在上面的已有技术作了详细说明。虽然传统Cu、Ni和Cr层的采用可能由经济状况决定，但特殊的防腐蚀层也可有变化。层12的厚度也可依据所用的特殊材料而变化。作为实施例，氰化物电镀铜、耐酸铜、双相镍和铬的结合层的最小厚度为约35毫米和标称厚度为约48毫米。
在外部装饰涂层的下面为由Zr和/或Ti的化合物形成的冲击层或粘结层14。层14的最小厚度约为0.025毫米，标称厚度为约0.05毫米。
颜色层16提供所需的装饰色，这在已有的技术中已经作了详细的介绍。铜色的颜色层的组分列于表1。
叠加于颜色层16上的是薄透明层18，它至少起两个作用，且其第一组分到第二组分是变化的。在特别有利的实施例中，过渡层的第一个作用是提供可接受的防腐蚀性能，第二个作用是保持颜色层16的颜色不变。在此例中，第一组分优选纯金属，最优选，沉积纯Zr(即在PVD室中释放真空之前)。第二组分优选为颜色层。从第一组分到第二组分的过渡发生在距离为约20～200处。
在下面的表1中，配方1公开了铜颜色层16的一组PVD沉积条件，而配方2公开了增加薄透明层18后的相同铜颜色层16的一组沉积条件。
材料科学领域的技术人员根据图2会预测到，在暴露于氧气气氛之前，就配方2来说，靠近涂覆制品表面的组分会不同于层16和18，层16在深度约为15O处开始，而从0～150的深度则为层18。他们还可进一步预测到，当暴露在空气中时，由于表面氧化会使表面由于添加氧和碳而改性，添加的碳也叫“偶然的”碳。偶然的碳会沉积在原始表面而氧则会进入原始表面并在其中进行化学结合以及被吸收到其中。原始表面组成的形态，如图2所示，也可以如图3所示被改性。
实施例表1
 PVD面漆配方(HTC1500装置) 1 2
 颜色(L*、a*、b*) 65.6，+9.3，+12.0 64.9，+10.4，+12.2
 目标物质 Zr Zr
基体 压铸Zn，镀铬，SC2(ASTMB456) 压铸Zn，镀铬，SC2(ASTMB456)
颜色层沉积参数  时间(mins) 25 24
 1阴极电流(A) 120 120
 2.乙炔流(sccm) 43 43
 3.氮气流(sccm) 400 400
 4.氩气流(sccm) 800 800
 5.基体偏压(V) 15 15
 6.最终厚度() 3400 3260
过渡层沉积参数过渡在1分钟周期内平稳完成  1阴极电流(A) 无 开始时 结束时
2.乙炔流(sccm) 120  120
43 0
3.氮气流(sccm) 400 0
 4.氩气流(sccm) 800  1200
 5.基体偏压(V) 15  70
 最终盐喷洒腐蚀试验结果(通过/试样尺寸)(24小时AASS，ASTMB117) 0/20 20/20
在图4中的结果为通过将使用上表的PVD配方2加工的实际制品的元件组分的角溶解XPS表面分析研究所得的图表。试验结果表明存在的表面结构如图3所示。
薄膜制造领域的技术人员会认为薄膜在一定的厚度下，该厚度依赖于折射率，但一般大于150一般是“光学稠密的”，即可能与可见光结合。本领域的技术人员也认可很薄的防腐蚀膜是已知的，但即使是为了防腐蚀的金薄膜的厚度一般也大于200因此根据已有技术，为了避免不希望的颜色变化，薄层18就需要小于约150，但矛盾的是，为了得到所需所的防腐蚀性能，同一薄层又需要其厚度至少大于200。这就是当薄膜同时要实现几种功能时经常碰到的矛盾和功能对薄膜厚度或其它性能限制的矛盾的例子。
参考在表1、图3和4中公开的薄过渡层的实际结构，考虑到其厚度为150，增加的薄过渡层18不能改变铜色层16的颜色并不出人意料。但是，非常不希望的是，薄过渡层完全消除严重腐蚀的缺陷。
腐蚀防护本质上是由纯Zr的表面组分(第一组分)提供的。第二组分，Zr渐少而增加了N和C以确保颜色层16赋予的颜色不会从本质上改变。由于过渡层18组分变化的特性，在薄过渡层18和颜色层16之间边界的有效部分的光现象和腐蚀现象就会不同。过渡层18的组分从表面上基本纯的Zr逐渐减少Zr量而增加N和C量的变化从本质上确定了的两种组分。第一组分靠近表面而第二组分远离表面。第一组分提供腐蚀防护而第二组分确保层的整个厚度以避免由层16产生的颜色的不适宜变化。
过渡层18的组分变化，如图2和3所示，可以是平稳的，逐渐的或均匀的。也可是一步一步的。
虽然如图2和3以及表1所示，加工制品的颜色来自颜色层16，而且由于过渡层18的性质，表面颜色是可见的，但是由过渡层18改变较大的颜色也落入本发明的范围，更具体的说，从大约90开始至150的过渡层部分。这也有可能在限定化学组成上不同于图2和图3，但是很清楚这也在本发明地范围内。在两者之一的任何情况下，过渡层中第二组分的作用是决定加工制品表面的可见色，无论其来自层16或过渡层18的一部分。在不改变本发明的条件下，层16和18之间也可包括厚度高达400的一个或多个无色透明薄层，例如二氧化硅或氧化铝。
在本发明的优选具体实施例中，过渡层的耐高温金属是Zr、Ti、Hf或它们的合金，这些物质由于部分具有防腐蚀功能而另一部分具有使在表面能够看见层16下的颜色的特性而适合作为过渡层。另外，第一组分中的金属可以选自金、银、铂和铂族金属的贵金属或它们的合金。此外，铬或不锈钢也可适当地起到过渡层金属原料的作用，
虽然本发明的优选形式已经在此展示和描述，但必须说明它还可有另外的许多改进、替代和选择。

Claims (17)

1.一种制品，其至少一部分表面上有一层由含金属物料组成的薄过渡层和具有从第一组分到第二组分变化的组分，此过渡层的功能不止一种。
2.如权利要求1的制品，其中的过渡层叠加在含金属的颜色层的上面。
3.如权利要求2的制品，其中在过渡层和含金属颜色层之间插入一层或多层的中间层，所述的中间层是无色、透明的，而且厚度小于400。
4.如权利要求1的制品，其中的第一组分选自由Ti、Zr或Hf组成的一组非贵重的耐高温金属或它们的一种合金。
5.如权利要求1的制品，其中的第一组分选自由金、银、铂、铂族金属组成的一组贵金属或它们的一种合金。
6.  如权利要求1的制品，其中的第一组分为选自由Cr或不锈钢组成的一组耐蚀金属或它们的一种合金，
7.如权利要求2的制品，其中的含金属颜色层与过渡层中的第二组分含有相同的组分。
8.如权利要求2的制品，其中的含金属颜色层的组分选自Zr、Ti、Hf、C和N中的一种或多种。
9.如权利要求2的制品，其中的第一组分是锆金属，第二组分选自Zr、Ti、Hf、C和N中的一种或多种。
10.如权利要求1的制品，其中的过渡层通过PVD工艺沉积。
11.如权利要求8的制品，其中的含金属颜色层通过PVD工艺沉积。
12.如权利要求1的制品，其中过渡层在第一组分和第二组分之间的过渡是平稳的。
13.如权利要求1的制品，其中在过渡层中从第一组分到第二组分的过渡是不连续的步骤。
14.如权利要求1的制品，其中过渡层的第一个目的是相对可见光实质上是透明和无色的，过渡层的第二个目的是提供抗腐蚀性能。
15.一种加工制品，至少在其表面的一部分有一层由含金属物料组成的薄过渡层，该含金属物料的组分从第一外部组分到外部组分下面的第二组分逐渐变化，其中的第一组分至少一部分有腐蚀防护作用，其中的第二组分决定过渡层涂覆的制品表面部分的可见色。
16.如权利要求15的制品，其中的过渡层叠加在含金属颜色层上，过渡层的第二组分实质上是透明的。
17.如权利要求15的制品，其中过渡层涂覆的制品表面部分的可见色决定于第二组分。
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CN102534487A (zh) * 2010-12-30 2012-07-04 鸿富锦精密工业（深圳）有限公司 具有硬质涂层的被覆件及其制备方法
CN102958310A (zh) * 2011-08-31 2013-03-06 光宝移动有限公司 制造电子装置的盖部件的方法
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CN103789766B (zh) * 2014-02-28 2016-01-06 厦门建霖工业有限公司 一种abs塑料表面金属层及其制备方法
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