CN1460066A - 具有不锈钢外观的涂敷制品 - Google Patents

具有不锈钢外观的涂敷制品 Download PDF

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Publication number
CN1460066A
CN1460066A CN02801088A CN02801088A CN1460066A CN 1460066 A CN1460066 A CN 1460066A CN 02801088 A CN02801088 A CN 02801088A CN 02801088 A CN02801088 A CN 02801088A CN 1460066 A CN1460066 A CN 1460066A
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China
Prior art keywords
layer
refractory metal
goods
nickel
nitrogen
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CN02801088A
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English (en)
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陈国存
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Vapor Technologies Inc
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Vapor Technologies Inc
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Publication of CN1460066A publication Critical patent/CN1460066A/zh
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
    • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/66—Copper alloys, e.g. bronze
    • C—CHEMISTRY; METALLURGY
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • C—CHEMISTRY; METALLURGY
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    • C23C14/0021—Reactive sputtering or evaporation
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

采用具有不锈钢外观的多层装饰和保护性涂层涂敷的制品(图2)。该涂层包括在所述制品表面上的一个或多个电镀层和在电镀层上的气相沉积的堆叠层，该堆叠层包括与包含耐火金属或耐火金属合金、氮气和氧气的反应产物的层交替的耐火金属或金属合金的层；其中这些反应产物的总氮和氧含量为约4－约32原子百分比和氮含量至少为约3原子百分比。

Description

具有不锈钢外观的涂敷制品
                        发明领域
本发明涉及采用具有不锈钢外观或颜色的多层装饰和保护性涂层涂敷的制品，特别是黄铜制品。
                        发明背景
目前对于各种黄铜制品如龙头、龙头罩、门旋钮、门把手、门锁眼盖等的实际情况是首先擦亮和抛光制品的表面到高光泽和然后涂敷保护性有机涂层(如由丙烯酸类、聚氨酯类、环氧类等组成的涂层)到此抛光的表面上。此体系的缺点是擦亮和抛光操作的劳动强度较大，特别是如果制品具有复杂的形状。同样，已知有机涂层并不总是如所需耐用的，和易于受酸的侵蚀。因此，如下情况是相当有利的：如果黄铜制品，或事实上其它制品，塑料、陶瓷、或金属，可以含有提供制品装饰性外观以及提供耐磨性、抗磨性和耐腐蚀性的涂层。在本领域已知的是可以将多层涂层涂敷到制品上，它提供装饰性外观以及提供耐磨性、抗磨性和耐腐蚀性。此多层涂层包括由耐火金属氮化物如氮化锆或氮化钛组成的装饰和保护性颜色层。此颜色层，当它是氮化锆时，提供黄铜色，和当它是氮化钛是提供金色。
U.S.专利Nos.5,922,478，6,033,790和5,654,108尤其描述了这样的涂层，它提供具有装饰性颜色的制品，如抛光的黄铜，且也提供耐磨性、抗磨性和耐腐蚀性。如果可以提供这样的涂层是非常有利的，该涂层提供与包含氮化锆或氮化钛的涂层基本相同的性能但不是黄铜色的或金色的，是不锈钢色的。本发明提供这样的涂层。
                          发明概述
本发明涉及含有沉积在制品的至少一部分表面上的装饰和保护性多层涂层的制品如塑料、陶瓷或金属制品。更特别地，本发明涉及含有沉积在其表面上特定具体类型材料的多个重叠层的制品或基材，特别是金属制品如铝、黄铜或锌。涂层是装饰性的和也提供耐腐蚀性、耐磨性和抗磨性。涂层提供不锈钢外观，即具有不锈钢颜色色调。因此，在其上含有涂层的制品表面模拟了不锈钢表面。
制品首先含有沉积在它的表面上的一个或多个电镀层。然后在电镀层的顶部，通过气相沉积如物理气相沉积，沉积夹层或堆叠层。直接沉积在基材表面上的第一层由镍组成。第一层可以是单一的或它可以由两个不同的镍层例如，直接沉积在基材表面上的半光亮镍层和重叠在半光亮镍层上的光亮镍层组成。在电镀层上是保护性夹层或堆叠层，该夹层或堆叠层由以下组成：与包含耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物的层交替的包含耐火金属或耐火金属合金的层。在夹层或堆叠层上是由耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物组成的颜色层。耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物是耐火金属或耐火金属合金、氧气和氮气的反应产物，其中氮和氧含量较低，即，低于化学计量。这些耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物的总氮和氧含量为约4-约32原子百分比和氮含量至少为约3原子百分比，优选约5-约28原子百分比和氮含量至少为约4原子百分比。
                         附图简述
图1是含有多层涂层的基材一部分的不按比例的横截面图，多层涂层包括双镍基础涂层，在顶部镍层上的保护性夹层或堆叠层和在堆叠层上的颜色层；
图2是相似于图1的视图，区别在于在顶部镍层和夹层或堆叠层中间存在耐火金属或耐火金属合金的触击层(strike layer)；
图3是相似于图2的视图，区别在于在顶部镍层和堆叠层中间存在铬层；和
图4是相似于图3的视图，区别在于在颜色层上存在耐火金属氧化物或耐火金属合金氧化物层。
                     优选实施方案的描述
制品或基材12可以由如下物质组成：可以在其上涂敷镀敷层的任何材料，如塑料，如ABS、聚烯烃、聚氯乙烯、和酚醛树脂，陶瓷，金属或金属合金。在一个实施方案中，它由金属或金属合金如铜、钢、黄铜、锌、铝、镍合金等组成。
在本发明中，如图1-4所示，通过镀敷如电镀将第一层或系列层涂敷到制品表面上。通过气相沉积将第二层或系列层涂敷到电镀层的表面上。电镀层尤其用作使制品表面变平的基础涂层。在本发明的一个实施方案中，可以在制品表面上沉积镍层13。镍层可以是由镀敷沉积的任何常规镍，如光亮镍、半光亮镍、缎光镍等。可以通过常规和公知的电镀工艺将镍层13沉积在基材12的至少一部分表面上。这些工艺包括使用常规的电镀浴，例如，Watts浴作为镀敷溶液。典型地这样的浴包含硫酸镍、氯化镍、和溶于水的硼酸。也可以使用所有的氯化物、氨基磺酸盐和氟硼酸盐镀敷溶液。这些浴可非必要地包括许多公知和通常使用的化合物如流平剂、增白剂等。为生产镜面光亮镍层，将至少一种类别I的增白剂和至少一种类别II的增白剂加入到镀敷溶液中。类别I增白剂是包含硫的有机化合物。类别II增白剂是不包含硫的有机化合物。类别II增白剂也可引起变平，且当加入到没有含硫的类别I增白剂的镀敷浴中时，导致半光亮镍沉积物。这些类别I增白剂包括烷基萘和苯磺酸、苯和萘二和三磺酸、苯和萘磺酰胺、和磺酰胺如糖精、乙烯基和烯丙基磺酰胺和磺酸。类别II增白剂一般是不饱和有机材料，例如，炔属或烯属醇、乙氧基化和丙氧基化炔属醇、香豆素、和醛。这些类别I和类别II增白剂对于本领域技术人员是公知的和容易购得。它们尤其描述在U.S.专利No.4,421,611中，该文献在此引入作为参考。
镍层可以由单一层如半光亮镍、缎光镍或光亮镍组成，或它可以是包含两个不同镍层，例如，由半光亮镍组成的层和由光亮镍组成的层的双层。镍层的厚度一般有效使制品的表面变平且提供改进的耐腐蚀性。此厚度一般为从约2.5μm，优选约4μm到约90μm。
如在本领域已知的那样，在基材上沉积镍层之前，通过放入常规和公知的酸浴，将基材进入酸活化。
在如图1-4所示的一个实施方案中，镍层13实际上由两个不同镍层14和16组成。层14由半光亮镍组成而层16由光亮镍组成。此双镍沉积物对其下的基材提供改进的耐腐蚀性。通过常规电镀工艺直接在基材12表面上沉积半光亮、无硫板14。然后将包含半光亮镍层14的基材12放入光亮镍镀敷浴中和在半光亮镍层14上沉积光亮镍层16。
半光亮镍层和光亮镍层的厚度是至少有效提供改进耐腐蚀性和/或制品表面流平的厚度。一般情况下，半光亮镍层的厚度至少为约1.25μm，优选至少约2.5μm，和更优选至少约3.5V。厚度上限一般不是关键的且由次要的如成本的考虑来支配。然而，一般情况下，不应当超过约40μm，优选约25μm，和更优选约20μm的厚度。光亮镍层16的厚度通常至少为约1.2μm，优选至少约3μm，和更优选至少约6μm。光亮镍层的厚度上限范围不是关键的且一般由如成本的考虑控制。然而，一般情况下，不应当超过约60μm，优选约50μm，和更优选约40μm的厚度。光亮镍层16也用作流平层，它倾向于覆盖或填充基材中的缺陷。
在一个实施方案中，如图3和4所示，位于镍层13和气相沉积层之间的是一个和多个另外的电镀层21。这些另外的电镀层包括但不限于铬、锡-镍合金等。当层21由铬组成时，它可以通过常规和公知的铬电镀技术沉积在镍层13上。这些技术与各种铬镀敷浴一起公开于Brassard，“装饰性电镀-转变中的工艺”，Metal Finishing，105-108页，1988年6月；Zaki，“铬镀敷”，PF Directory，146-160页；和U.S.专利Nos.4,460,438、4,234,396和4,093,522中，所有这些文献在此引入作为参考。
铬镀敷浴是公知和可购得的。典型的铬镀敷浴包含铬酸或其盐，和催化剂离子如硫酸根或氟离子。催化剂离子可以由硫酸或其盐和氟硅酸提供。该浴可以在约112-116°F的温度下操作。典型地在铬镀敷中，在约5-9伏下采用约150安培每平方英尺的电流密度。
铬层的厚度一般至少为约0.05μm，优选至少约0.12μm，和更优选至少约0.2μm。一般情况下，厚度上限一般不是关键的且由次要的如成本的考虑来决定。然而，铬层的厚度不应当超过约1.5μm，优选约1.2μm，和更优选约1μm。
代替由铬组成的层21，它可以由锡-镍合金，即锡和镍的合金组成。锡-镍合金可以通过常规和公知的锡-镍电镀工艺沉积在基材表面上。这些工艺和镀敷浴是常规和公知的，且尤其公开于U.S.专利Nos.4,033,835、4,049,508、3,887,444、3,772,168和3,940,319中所有这些文献在此引入作为参考。
锡-镍合金层优选由代表原子组成SnNi的约60-70wt％锡和约30-40wt％镍，更优选约65％锡和35％镍组成。镀敷浴包含足够量的镍和锡以提供上述组成的锡-镍合金。
市售的锡-镍镀敷工艺是购自ATOTECH的NiColloyTM工艺，和描述在它们的技术信息表No：NiColloy，1994年10月30日，该文献在此引入作为参考。
锡-镍合金层21的厚度一般至少为约0.25μm，优选至少约0.5μm，和更优选至少约1.2μm。厚度上限范围一般不是关键的且一般依赖于经济考虑。一般情况下，不应当超过约50μm，优选约25μm，和更优选约15μm的厚度。
在电镀层上，通过气相沉积如物理气相沉积和化学气相沉积，优选物理气相沉积，至少沉积由如下组成的夹层或堆叠层32：与由耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物组成的层36交替的包括耐火金属或耐火金属合金的层34。
包括耐火金属或耐火金属合金的层34包括铪、钽、钛、锆、锆-钛合金、锆-铪合金等，优选铪、钛、锆或锆-钛合金。
包括耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物的层36是耐火金属或耐火金属合金、氧气和氮气的反应产物。在这些耐火金属含氮和氧化合物和耐火金属合金含氮和氧化合物中，总氮和氧含量为约4-约32原子百分比，优选约5-约28原子百分比。因此，例如，氮含量是6原子百分比和氧含量是20原子百分比，氮含量是8原子百分比和氧含量是8原子百分比，氮含量是15原子百分比和氧含量是2原子百分比。氧的存在量一般至少为约1原子百分比。
这些反应产物的氮含量一般尤其对具有不锈钢颜色的涂层有影响。氮含量为至少约3原子百分比到约22原子百分比，优选至少约4原子百分比到约16原子百分比。氮含量不应当超过约22原子百分比，优选约16原子百分比，或涂层损失了它的不锈钢外观和开始具有镍颜色。因此，氮含量对于具有不锈钢颜色的涂层是关键的。
耐火金属或耐火金属合金、氮气和氧气的反应产物一般由耐火金属氧化物或耐火金属合金氧化物，金属氮化物或耐火金属合金氮化物，和耐火金属氧-氮化物或耐火金属合金氧-氮化物组成。因此，例如，锆、氧气和氮气的反应产物包括氧化锆，氮化锆和氧-氮化锆。包括氧化锆和氮化锆的这些金属氧化物和金属氮化物和它们的制备和沉积是常规和公知的，和尤其公开于U.S.专利No.5,367,285中，该文献的公开内容在此引入作为参考。
夹层或堆叠层32的平均厚度一般为约500埃-约1μm，优选约0.1μm-约0.9μm，和更优选约0.15μm-约0.75μm。夹层或堆叠层一般包含约4-约100个交替层34和36，优选约8-约50个交替层34和36。
每个层34和36的厚度一般至少为约15埃，优选至少约30埃，和更优选至少约75埃。一般情况下，层34和36应当不厚于约0.38μm，优选约0.25μm，和更优选约0.1μm。
形成堆叠层32的方法是通过采用溅射或阴极弧蒸发以沉积耐火金属如锆或钛的层34，随后通过反应性溅射或反应性阴极弧蒸发以沉积耐火金属含氮和氧化合物或金属合金含氮和氧化合物的层36。
优选在气相沉积如反应性溅射期间，在零(不引入气体)到在所需值下引入气体之间改变(脉冲)氮气和氧气的流量，以在夹层32中形成耐火金属或耐火金属合金的层36和耐火金属或耐火金属合金、氮气和氧气的反应产物的层34的多个交替层。
在夹层或堆叠层32上是颜色层38。颜色层38由耐火金属或耐火金属合金、氮气和氧气的反应产物组成，其中该反应产物的总氧和氮含量为约5-约32原子百分比和氮含量为至少约4原子百分比，优选约6-约28原子百分比和氮含量至少为约5原子百分比。颜色层38由与层36相同的含氮和氧化合物组成。颜色层38的厚度至少有效提供颜色，更具体地提供不锈钢颜色。一般情况下，此厚度至少为约25埃，和更优选至少约500埃。厚度上限范围通常不是关键的和依赖于次要的考虑如成本。一般情况下不超过约0.75μm，优选约0.65μm，和更优选约0.5μm的厚度。
改变颜色层38中的氧含量会使不锈钢颜色更带蓝色或带黄色。增加氧含量会使颜色层具有带蓝色的色调。降低氧含量会使颜色层具有带黄色的色调。
除夹层或堆叠层32和颜色层38以外，可以非必要地存在另外的气相沉积层。这些另外的气相沉积层可包括由在堆叠层32和电镀层之间沉积的耐火金属或耐火金属合金组成的层。耐火金属包括铪、钽、锆和钛。耐火金属合金包括锆-钛合金、锆-铪合金和钛-铪合金。耐火金属层或耐火金属合金层31一般尤其用作改进夹层32对电镀层粘合的触击层。如图2-4所示，耐火金属或耐火金属合金触击层31一般位于夹层32和电镀层中间。层31的厚度一般至少有效使层31用作触击层，即，用以改进堆叠层32对其下的电镀层的粘合。一般情况下，此厚度至少为约60埃，优选至少约120埃，和更优选至少约250埃。厚度上限范围不是关键且一般依赖于如成本的考虑。然而，一般情况下，层31应当不厚于约1.2μm，优选约0.5μm，和更优选约0.25μm。
通过常规和公知的气相沉积技术包括物理气相沉积技术如阴极弧蒸发(CAE)或溅射，沉积耐火金属或耐火金属合金层31。溅射技术和设备尤其描述于J.Vossen和W.Kern的“薄膜工艺II”，Academic Press，1991；R.Boxman等人，“真空弧科学和技术手册”，Noyes Pub.，1995；和U.S.专利Nos.4,162,954和4,591,418中，所有这些文献在此引入作为参考。
简单地，在溅射沉积工艺中，将耐火金属(如钛或锆)目标(它是阴极)和基材放入真空腔室中。将腔室中的空气抽空以在腔室中产生真空条件。将惰性气体，如氩气引入腔室。将气体粒子电离和向目标加速以移除钛或锆原子。然后将移除的目标材料典型地作为涂膜沉积在基材上。
在阴极弧蒸发中，将典型地几百安培的电弧撞击在金属阴极如锆或钛的表面。弧蒸发阴极材料，它然后冷凝在基材上，形成涂层。
在本发明的优选实施方案中，耐火金属由钛、铪或锆组成，和耐火金属合金由锆-钛合金组成。
另外的气相沉积层也可包括不是上述耐火金属或耐火金属合金、氧气和氮气反应产物的耐火金属化合物和耐火金属合金化合物。这些耐火金属化合物和耐火金属合金化合物包括耐火金属氧化物和耐火金属合金氧化物，耐火金属碳化物和耐火金属合金碳化物，耐火金属氮化物和耐火金属合金氮化物，和耐火金属碳氮化物和耐火金属合金碳氮化物。
在本发明的一个实施方案中，如图4所示，在颜色层38上沉积由耐火金属氧化物或耐火金属合金氧化物组成的层39。该层39的耐火金属氧化物和耐火金属合金氧化物包括，但不限于氧化铪、氧化钽、氧化锆、氧化钛、和锆-钛合金氧化物，优选氧化钛、氧化锆、和锆-钛合金氧化物。这些氧化物和它们的制备是常规和公知的。
层39有效向涂层提供改进的耐化学品，如酸或碱的性能。包含耐火金属氧化物或耐火金属合金氧化物的层39的厚度一般至少有效提供改进的耐化学品性能。一般情况下此厚度至少为约10埃，优选至少约25埃，和更优选至少约40埃。层39应当足够薄使得它并不使其下的颜色层38的颜色变暗。即层39应当足够薄使得它是非不透明的或基本透明的。一般情况下层39应当不厚于约0.10μm，优选约250埃，和更优选约100埃。
可以通过指定的不锈钢颜色标准控制或预定涂层的不锈钢颜色。在其中颜色层38由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的情况下，可以通过总气体流中氮气对氧气比例的增加或减少，将不锈钢颜色调节到轻微更带黄色或带蓝色。可以完全地匹配于不锈钢的抛光或刷光表面润饰。
为更容易理解本发明，提供以下实施例。该实施例是说明性且并不将本发明限定于此。
                          实施例1
将黄铜龙头放入包含标准和公知的肥皂、洗涤剂、抗絮凝剂等的常规浸泡清洁剂浴中，将该浴保持在8.9-9.2的pH和180-200°F的温度下约10分钟。然后将黄铜龙头放入常规超声波碱性清洁剂浴中。该超声波清洁剂浴的pH为8.9-9.2，其被保持在约160-180°F的温度下，且其包含常规和公知的肥皂、洗涤剂、抗絮凝剂等。在超声波清洁之后，将龙头清洗和放入常规碱性电清洁剂浴中。该电清洁剂浴保持在约140-180°F的温度，约10.5-11.5的pH下，且其包含标准和常规的洗涤剂。然后将龙头清洗两次和放入常规酸活化剂浴中。酸活化剂浴的pH为约2.0-3.0，其处于环境温度下，且包含氟化钠基酸盐。然后将龙头清洗两次和放入光亮镍镀敷浴中约12分钟。光亮镍浴一般是保持在约130-150°F的温度，约4.0的pH下的常规浴，其包含NiSO4、NiCl2、硼酸、和增白剂。在龙头表面上沉积平均厚度为约10μm的光亮镍层。将光亮镍镀敷的龙头清洗三次和然后放入常规、可市购的的六价铬镀敷浴中，使用常规铬镀设备约7分钟。六价铬浴是常规和公知的浴，它包含约32盎司/加仑铬酸。该浴也包含常规和公知的铬镀敷添加剂。该浴保持在约112-116°F的温度下，且采用混合硫酸盐/氟化物催化剂。铬酸对硫酸盐比例是约200∶1。在光亮镍层表面上沉积约0.25μm的铬层。将龙头在去离子水中充分清洗和然后干燥。将铬镀敷的龙头放入阴极弧蒸发镀敷容器中。容器一般是包含真空腔室的圆筒形外壳，该真空腔室适于通过泵抽空。通过用于改变进入腔室氩气流量的可调节阀门，将氩气源连接到腔室。此外，通过用于改变进入腔室氮气和氧气流量的可调节阀门，将氮气和氧气源连接到腔室。
将圆筒形阴极安装在腔室中心且连接到可变D.C.电源的负输出上。将电源的正侧连接到腔室壁上。阴极材料包括锆。
将镀敷的龙头安装在转轴上，将16个这样的转轴安装在围绕阴极外部的环上。整个环围绕阴极旋转而每个转轴也围绕它自身的轴旋转，导致所谓的行星运动，它对围绕每个转轴安装的多个龙头提供对阴极的均匀曝露。该环典型地在几个rpm下旋转，而每个转轴相对于每个环回转进行几个回转。转轴与腔室被电隔离且设置有可旋转接触使得可以在涂敷期间将偏压施加到基材上。
将真空腔室抽空到约10-5-10-7托的压力和加热到约150℃。
然后将电镀龙头进行高偏压弧等离子体清洁，其中将约500伏的(负)偏压施加到电镀龙头上同时将大约500安培的弧撞击和保持在阴极上。清洁的持续时间大约是5分钟。
在足以保持约1-5毫托压力的速率下引入氩气。在3分钟时间期间内，在铬镀敷龙头上沉积平均厚度为约0.1μm的锆层。阴极弧沉积工艺包括施加D.C.电源到阴极上以达到约500安培的电流，向容器中引入氩气以保持容器中压力在1-5毫托下和以上述行星方式旋转龙头。
在沉积锆层之后，将保护性堆叠层涂敷到锆堆叠层上。在足以提供各自约5-约28原子百分比的总氮气和氧气含量的流量下，周期性地向真空腔室中引入氮气和氧气流。此氧气和氮气流是氩气、氮气和氧气总物流的约4-30％。在流动期间弧放电在大约500安培下持续。将氮气和氧气流量脉冲，即将它周期性地从总流量的约10％-20％和约零的流量改变。氮气和氧气脉冲的周期是1到2分钟(30秒到1分钟开启，然后关闭)。脉冲沉积的总时间是约15分钟，导致10-15个层的堆叠，每个层的厚度为约2.5埃-约75埃。
在沉积堆叠层之后，将氮气和氧气流量保留在足以提供各自约6-28原子百分比的总氮气和氧气含量的流量下。此氧气和氮气流量是氩气、氮气和氧气总流量的约4-约20％。将此物流持续约5-10分钟的时间以在堆叠层顶部形成颜色层。在沉积此颜色层之后，终止氮气流和将大约0.1标准升每分钟的氧气流持续30秒到1分钟的时间。形成厚度为约50埃-125埃的氧化锆薄层。在此最后沉积阶段结束时将弧熄灭，将真空腔室排气和取出涂敷制品。
尽管已经为了说明的目的描述了本发明的某些实施方案，应理解在本发明总的范围中可以有各种实施方案和改进。

Claims (15)

1.一种在其至少一部分表面上含有具有不锈钢外观的保护和装饰性涂层的制品，包括：
至少一个由镍组成的层；
由如下组成的堆叠层：与由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的层交替的由耐火金属或耐火金属合金组成的层；
由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的颜色层；
其中所述由耐火金属或耐火金属合金、氮气和氧气的反应产物的总氮和氧含量各自为约4-约22原子百分比和氮含量至少为约3原子百分比。
2.权利要求1的制品，其中所述氮和氧含量为约5-约28原子百分比和氮含量至少为约4原子百分比。
3.权利要求1的制品，其中由耐火金属或耐火金属合金组成的层在所述至少一个由镍组成的层上。
4.权利要求1的制品，其中由耐火金属氧化物或耐火金属合金氧化物组成的层在所述颜色层上。
5.权利要求3的制品，其中由耐火金属氧化物或耐火金属合金氧化物组成的层在所述颜色层上。
6.权利要求1的制品，其中由铬组成的层在所述至少一个由镍组成的层上。
7.权利要求6的制品，其中由耐火金属或耐火金属合金组成的触击层在所述由铬组成的层上。
8.权利要求7的制品，其中所述堆叠层在所述触击层上。
9.权利要求1的制品，其中由锡和镍合金组成的层在所述至少一个由镍组成的层上。
10.权利要求9的制品，其中耐火金属或耐火金属合金组成的触击层在所述至少一个由锡和镍组成的层上。
11.权利要求7的制品，其中所述堆叠层在所述触击层上。
12.权利要求1的制品，其中所述至少一个由镍组成的层由一个镍层组成。
13.权利要求1的制品，其中所述至少一个由镍组成的层由两个镍层组成。
14.权利要求1的制品，其中所述涂层具有刷光不锈钢润饰的外观。
15.权利要求1的制品，其中所述耐火金属选自锆、钛和铪。
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