CN1197995C - 带有装饰和保护覆层的制品 - Google Patents

带有装饰和保护覆层的制品 Download PDF

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Publication number
CN1197995C
CN1197995C CNB981096999A CN98109699A CN1197995C CN 1197995 C CN1197995 C CN 1197995C CN B981096999 A CNB981096999 A CN B981096999A CN 98109699 A CN98109699 A CN 98109699A CN 1197995 C CN1197995 C CN 1197995C
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China
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layer
zirconium
zirtan
titanium
goods
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Expired - Fee Related
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CNB981096999A
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CN1205365A (zh
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R·P·威尔特
J·H·彼得森
P·J·朱特
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Masco Corp
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Masco Corp
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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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • 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
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    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • 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
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    • 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
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    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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    • 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
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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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
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    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
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Abstract

一种制品，其表面有多层覆层，包括镍层、铬层、难熔金属层，较好的是锆层、由难熔金属化合物和难熔金属合金化合物层所组成的许多交替层构成的夹心层、较好的是氮化锆层以及难熔金属氧化物层、或由难熔金属、氧和氮的反应产物组成的层。该覆层为制品提供了抛光黄铜的颜色，也提供了耐磨保护、抗腐蚀保护，并提高了耐酸性。

Description

带有装饰和保护覆层的制品
本发明涉及带有多层装饰和保护覆层的基底，特别是黄铜基底。
目前对如灯具、三角架、烛台、门扭和手把等各种黄铜制品的处理方法是，首先把制品的表面打磨和抛光为一高光泽面，然后把一有机物保护覆层，如丙烯酸衍生物、尿烷、环氧化物等物质组成的保护层覆在抛光的表面上。这种方法通常能达到令人满意的效果，但这种系统存在着缺点，特别是当制品的形状复杂时打磨和抛光很费工。而且，已知的有机层并不总如希望的那样持久，而且易受酸的侵蚀。因此，如果能够为黄铜制品，或者其它制品，无论是塑料、陶瓷制品还是金属制品提供一种覆层，它不仅使制品呈现精抛黄铜的外观，还能起到耐磨并腐蚀保护的作用并提高耐酸性，这将是相当有益的。本发明提供了这样的覆层。
本发明目的在于提供一种制品，如塑料、陶瓷，或金属制品，最好是金属制品，其表面至少部分沉积有多层覆层。本发明尤其涉及制品或基底，特别是金属制品如不锈钢、铝、黄铜或锌，其制品表面沉积了一些特定类型的金属或金属化合物的许多重叠着的金属层。覆层有装饰作用，有抗腐蚀和抗磨作用，并提高了耐酸性能。该覆层提供了精抛黄铜的外观，即有黄铜色泽。因此，其上有覆层的制品表面与精抛黄铜的表面相似。
在该制品的一个实施方案中，首先在其表面沉积一个或多个电镀层。然后用汽相沉积法，将一个或多个沉积层沉积在电镀层的上面。在另一个实施方案中，不插入电镀层，汽相沉积层直接沉积在制品的表面。
在该实施方案中，在制品有一系列的一个或多个电镀层在其上的情况下，直接沉积在基底表面的第一层由镍组成。第一层可能是一单层或由两个不同的层组成，如直接沉积在基底表面的半光亮镍层和在半光亮镍层上的光亮镍层。沉积在镍层上的是由铬构成的层。在铬层上是一个由非贵重难熔金属或非贵重难熔金属合金组成的层，如锆、钛、铪和钽或锆钛合金，最好是锆、钛或锆钛合金层。在高熔点金属或金属合金层上面是由非贵重难熔金属化合物或非贵重难熔金属合金化合物，与非贵重难熔金属或非贵重难熔金属合金的交替层所组成的夹心层。在夹心层上是由非贵重难熔金属化合物或非贵重难熔金属合金化合物组成的层。在非贵重金属化合物或非贵重金属合金层的上面是，由非贵重难熔金属氧化物，非贵重难熔金属合金氧化物，或非贵重难熔金属或非贵重难熔金属合金与氧、氮的反应产物组成的层。
镍和铬层采用电镀法施加。非贵重难熔金属或非贵重难熔金属合金层、夹心层、非贵重难熔金属化合物或非贵重难熔金属合金化合物层和由非贵重难熔金属氧化物，非贵重难熔金属合金氧化物，或非贵重难熔金属或非贵重难熔金属合金与氧、氮的反应产物组成的层采用汽相沉积法如阴极电弧蒸汽法或喷射法施加。
图1是部分基底的横截面图，该图不按比例，基底的表面有电镀和汽相沉积法沉积的多层覆层。
图2是与图1类似的图，但把汽相沉积覆层直接覆在制品的表面，而不插入电镀层。
制品或基底12可以由任何可镀的材料如塑料、陶瓷、金属或金属合金组成，最好是由可镀的金属或金属合金如铜、钢、黄铜、锌、铝、镍合金等组成。在较佳实施方案中基底是黄铜或锌。
在本发明的一实施方案中，如图1所示，第一系列的层用电镀法覆在制品的表面上。第二层用汽相沉积法镀在电镀层的表面上。在这个实施方案中，镍层13可以用常规公知的电镀法沉积在基底12上。这些方法包括使用常规的电镀液如Watts镀液作为镀液。这类镀液包含溶解在水中的硫酸镍、氯酸镍和硼酸。所有的氯化物、磺酰胺及氟硼酸镀液都可以使用。可以任意包括公知的常规使用的化合物如均化剂、光亮剂等。为了产生镜面状的光亮镍层，应将至少一种I级光亮剂和至少一种II级光亮剂加入到镀液中。I级光亮剂是包含硫的有机化合物。II级光亮剂是不包含硫的有机化合物。II级光亮剂也能起到均匀化作用，当被加入到没有含硫的I级光亮剂的电镀液中时，会产生半亮的镍沉积物。I级光亮剂包括烷基萘和苯磺酸、苯和萘的二磺酸和三磺酸、苯和萘的氨磺酰胺、如邻磺酰苯甲酰亚酰之类的磺酰胺、乙烯基和丙烯基氨磺酰胺和磺酸。II级光亮剂通常是不饱和有机材料如炔醇或烯醇、乙氧基化的炔醇和丙氧基化的炔醇、香兰素和醛类。
这些I级和II级光亮剂已为普通技术人员所熟知，并在市上可容易得到。它们在美国专利No4421611中被说明，此专利内容经参考已结合在本文中。
镍层可以是一单层比如由半光亮镍组成或由光亮镍组成，或者是包含两个不同的层的一个双层，如由半光亮镍层和光亮镍层组成的双层。镍层的厚度通常是在约0.000100英寸到约0.0035英寸之间，最好是在约0.000150英寸到约0.0035英寸之间。
如普通技术人员知道的那样，在镍层沉积在基底表面以前，将基底放在传统的公知的酸性镀液中，受到酸的活化作用。
在如图1中所说明的，在实施方案中，镍层13实际上由两个不同的镍层14和16组成。层14由半光亮镍组成而层16由光亮镍层组成。这个双层的镍层增强了对底基底的防腐蚀保护能力。半亮不含硫的层14用常规的电镀法直接沉积在基底12上。然后，将包含半光亮镍层14的基底12放在光亮镍镀液中，这样光亮镍层就沉积在半光亮镍层14上了。
半光亮镍层厚度和光亮镍层厚度要对防腐保护是有效。通常，半光亮镍层厚度至少约0.00005英寸，较好的至少约0.0001英寸，最好至少约0.00015英寸。该厚度的上限通常并不重要，它取决于对次要因素，如成本的考虑。但是，通常不应超过约0.0015英寸的厚度，较好的不超过约0.001英寸，最好不超过约0.00075英寸。光亮镍层16一般的厚度至少约0.00005英寸，较好的至少约0.000125英寸，最好的至少约0.00025英寸。光亮镍层的厚度上限不重要，一般是由成本等因素控制。但是，该厚度通常不超过约0.0025英寸，较好的不超过约0.0002英寸，最好不超过约0.0015英寸。光亮镍层16也可以起到均匀化层的作用，它能覆盖或填充在基底中的缺陷。
在镍层13之上，最好是光亮镍层16之上沉积的是由铬组成的层21。可以用常规的公知电镀铬技术把铬层21沉积在层16上。这些电镀技术和各种镀铬液一起已在Brassard的“Decorative Electroplating-A Process in Transition”，(Metal Finishing，pp105-108，June 1988)；Zaki的“Chromium Plating”，(PF Diretory，pp146-160)和美国专利No.4460438、No.4234396、No.4093522中公开，以上文献的内容经参照结合在本文中。
镀铬液是公知的和市售的。典型的镀铬液包含铬酸或铬酸盐，和催化剂离子如硫酸盐或氟化物。这类催化剂离子可由硫酸及其盐和氟硅酸提供。该镀液的操作温度约112-116°F。一般在铬镀液中电流密度约150安培/英尺，电压约5-9伏特。
铬层的厚度一般至少是约0.000002英寸，较好是约至少0.000005英寸，最好是约至少0.000008英寸。该厚度的上限通常并不重要，它取决于对次要因素，如成本的考虑。但是，该厚度通常不应超过约0.00006英寸，较好是不超过约0.00005英寸，最好是不超过约0.00004英寸。
沉积在铬层21上的是层22，它由非贵重难熔金属或金属化合物，如铪、钽、锆、钛如锆钛合金，较好是锆、钛或锆钛合金，最好是锆组成。
用常规公知的技术，包括汽相沉积法，如阴极弧蒸镀(CAE)或溅射法等，将22层沉积在21层上。溅射技术和装置在J.Vossen and W.Kern的“ThinFilm ProcessesII”，(Academic Press，1991)；R.Boxman et al的“Handbook ofVacuum Arc Science and Technology”，(Noyes Pub.，1995)；和美国专利No.4162954和No.4591418中已公开，以上文献内容经参照已结合于本文中。
简要地说，在溅射离子沉积法中，将难熔金属(如钛或锆)即阴极，和基底放在真空室中。室内的空气被抽出以便在室中形成真空条件。将惰性气体如氩引入室中。气体颗粒被电离并被加速至该靶，从而撞出钛或锆原子，然后，被撞出的靶材作为覆层沉积在基底表面。
在阴极弧蒸镀法中，几百个安培的电弧碰撞在金属阴极，如锆或钛的表面上。电弧蒸发了阴极物质，该物质沉积在基底的表面形成覆层。
层22的厚度一般是至少约0.00000025英寸，较好是约至少0.0000005英寸，最好是约至少0.000001英寸。该厚度的上限通常并不重要，它取决于对次要因素，如成本的考虑。但是，层22的厚度通常不应超过约0.00005英寸，较好是不超过约0.000015英寸，最好是不超过约0.000010英寸。
在本发明的较佳方案中，层22由钛、锆或锆钛合金，最好是锆组成。用溅射或阴极电弧汽相法沉积该层。
夹心层26由非贵重难熔金属化合物或非贵重难熔金属合金化合物28，和非贵重难熔金属或非贵重难熔金属合金30组成，层28和层30沉积在难熔金属或难熔金属合金，如锆或锆钛合金层22上。此结构在图1和图2中被说明，其中，层22代表难熔金属或难熔金属合金，最好是锆或锆钛合金层。26代表夹心层，28代表非贵重难熔金属化合物层或非贵重难熔金属合金化合物层，30代表非贵重难熔金属层或非贵重难熔金属合金层。
层30所含的非贵重难熔金属和非贵重难熔金属合金，包括铪、钽、钛、锆、锆钛合金、锆铪合金等，较好是锆、钛或锆钛合金，最好是锆或锆钛合金。
层28所含的非贵重难熔金属化合物和非贵重金属合金化合物，包括铪化合物、钽化合物、钛化合物、锆化合物和锆钛合金化合物，较好是钛化合物、锆化合物或锆钛合金化合物，最好是锆化合物。这些化合物选自氮化物、碳化物和碳氮化物，最好从氮化物中选择。因此，钛化合物从氮化钛、碳化钛和碳氮化钛中选择，氮化钛最好。锆化合物从氮化锆、碳化锆和碳氮化锆中选择，氮化锆最好。
夹心层26的平均厚度至少约0.000002英寸到约0.00004英寸，较好是至少约0.000005英寸到约0.000035英寸，最好是至少约0.000006英寸到约0.00003英寸。
每个层28和层30的厚度一般至少是约0.00000001英寸，较好是至少约0.00000025英寸，最好是约至少0.0000005英寸。层28和层30的厚度通常不应超过约0.000015英寸，较好是不超过约0.00001英寸，最好是不超过约0.00005英寸。
形成夹心层26的方法是，用反应性离子溅射或反应性阴极弧蒸镀沉积非贵重难熔金属氮化物，如氮化锆或氮化钛的层28以后，用离子溅射或阴极弧蒸镀沉积非贵重难熔金属，如锆或钛的层30。
氮气的流速最好在汽相沉积如反应性溅射过程中在0值(无氮气引入)至需要引入的氮气量之间变化(脉冲)，从而在夹心层26中形成金属层30和金属氮化物层28的许多交替层。
在夹心层26中，由难熔金属层30和难熔金属化合物层26所组成的交替层的数量通常至少约2个，较好是至少约4个，最好是约6个。通常在夹心层26中，由难熔金属层30和难熔金属化合物层28所组成的交替层的数量不应超过约50，较好是不超过约40，最好是不超过约30。
在本发明的一个实施方案中，如图1和2所示，层32由非贵重难熔金属化合物或非贵重难熔金属合金化合物，较好是氮化物、碳化物或碳氮化物，最好是氮化物组成。用汽相沉积法将层32沉积在夹心层26上。
层32由铪化合物、钽化合物、钛化合物、锆钛合金化合物或锆化合物组成，较好是由钛化合物、锆钛合金化合物或锆化合物组成，最好是由锆化合物组成。钛化合物从氮化钛、碳化钛和碳氮化钛中选择，氮化钛最好。锆化合物从氮化锆、碳氮化锆和碳化锆中选择，氮化锆最好。
层32提供了耐磨性和需要的颜色或外观，如磨亮的黄铜外观。用任何公知的常规汽相沉积技术如反应性溅射法和阴极弧蒸镀法，将层32沉积在层26上。
除了引入了与被撞击的靶材发生反应的反应性气体，通常反应性阴极弧蒸镀和反应性溅射法类似于一般的溅射和阴极弧蒸镀法。因此，在氮化锆组成层32的情况下，阴极由锆组成，氮气作为反应性气体引入室中。通过控制与锆反应的氮气量，氮化锆的颜色能够调成类似于不同色调的黄铜的颜色。
层32的厚度至少要对提高耐磨性有效。通常该厚度至少是0.0000001英寸，更好是至少0.000001英寸，最好是0.000002英寸。该厚度的上限通常不重要，取决于对次要因素，如成本的考虑。一般该厚度不超过约0.00003英寸，不超过约0.000025英寸较好，最好不超过约0.000020英寸。
氮化锆是较好的覆层材料，因为它使制品的外观最接近抛光的黄铜。
在本发明的一个实施方案中，34层由非贵重难熔金属或非贵重难熔金属合金、与含有氧的气体，如氧和氮的反应产物组成，该层沉积在层32上。本发明中所用的的金属是能够在合适的条件下形成金属氧化物和金属氮化物的金属，该条件比如是在使用含有氧和氮的反应气体。这些金属可以是，如钽、铪、锆、锆钛合金和钛，较好的是钛、锆钛合金和锆，最好是锆。
金属或金属合金、氧和氮的反应产物通常由金属或金属合金氧化物、金属或金属合金氮化物和金属或金属合金氧氮化物组成。因此，比如，锆、氧和氮的反应产物包括氧化锆、氮化锆和氧氮化锆。这些包括氧化锆和氮化锆合金的金属氧化物和金属氮化物以及它们的制备和沉积是常规和公知的，并在美国专利No.5367285中公开，该文献经参照已结合于本文中。
层34可以用公知的常规气体沉积技术沉积，包括反应性溅射和阴极弧蒸镀。
另一实施方案是，代替了由难熔金属或难熔金属合金，与氧和氮的反应产物组成的层34的是，由非贵重难熔金属氧化物或非贵重难熔金属合金氧化物组成的层34。组成层34的难熔金属氧化物和难熔金属合金氧化物包括，但不限于氧化铪、氧化钽、氧化锆和氧化钛，较好是是氧化钽和氧化锆，最好是氧化锆。这些氧化物和他们的制备是常规的和公知的。
34层包括(i)非贵重难熔金属或非贵重难熔金属合金，与氧和氮的反应产物，(2)非贵重难熔金属氧化物或非贵重难熔金属合金氧化物，层34的厚度至少要对提高耐酸性有效。该厚度至少约0.00000005英寸，较好是至少约0.0000001英寸，最好是至少约0.00000015英寸。通常，层34的厚度不超过约0.000005英寸，不超过约0.000002英寸较好，最好不超过约0.000001英寸。
在实施方案中，如图2所示，将覆层22，26，32和34直接用汽相沉积法沉积在基底12的表面，没有插入电镀层。标号22，26，28，32和34与图1中的数字所代表的层相同。
为了更清晰地理解本发明，提供了下面的实施例。实施例是作为例证的，不限制本发明。
                           实施例1
将黄铜的龙头放入常规的恒温清洗液中10分钟，清洗液中含标准的公知的皂类、洗涤剂和软絮凝剂等，它们的PH值维持在8.9-9.2，温度在180-200°F。然后将此黄铜的龙头放入常规的超声碱性清洗液中。超声清洗液的PH值为8.9-9.2，温度约160-180°F，清洗液包含常规的公知的皂类、洗涤剂和软絮凝剂等。超声清洗以后将龙头漂洗并放在常规的碱性电清洗液中。电清洗液的温度维持在约140-180°F  ，PH值约10.5-11.5，含有标准的常规的洗涤剂。然后漂洗龙头两次，放入常规的酸性活化液中。酸性活化液的PH值约2.0-3.0，温度是室温，含有氟化钠为基的酸式盐。将龙头清洗两次，放在光亮镍镀液中约12分钟。通常，光亮镍镀液是常规的镀液，其温度在约130-150°F，PH值约4.0，含有NiSO4，NiCl2，硼酸和光亮剂。光亮镍层的平均厚度约0.0004英寸，该层沉积在龙头上。将镀过光亮镍层的龙头漂洗三次，然后放入常规的市售的采用常规的镀铬液装置的六价铬镀液中约7分钟。六价铬镀液是常规的公知的镀液，它含有约32盎斯/加仑的铬酸。此镀液中也包含常规的公知的铬镀添加剂。镀液的温度维持在约112-116°F，使用混合的硫酸盐/氟化物催化剂。铬酸与硫酸盐的比例约200∶1。厚度约0.00001英寸的铬层沉积在光亮镍层的表面。在去离子水中将龙头彻底清洗然后干燥。将镀过铬的龙头放在阴极电弧蒸发镀容器中。通常该容器是一个圆柱形箱，它有一适于通过泵抽真空的真空室。氩气源经调节阀与真空室连接，调节阀改变进入室中的氩气流量。氮气源也经调节阀与室相连，用调节阀改变进入室中的氮气流量。
将圆柱形的阴极装在室中心并与可变的直流电源的负输出端相连。电源的正极与室壁相连。阴极物质含有锆。
将龙头装在一些杆上，16个杆装在在阴极周围的园环上。每个杆围绕其轴旋转的同时，整个圆环围绕阴极旋转，产生所谓的行星运动，该运动使每一个装在杆上的龙头对阴极有均匀的暴露。圆环以每分钟几转的速度旋转，而圆环转一次，每个杆转几次。杆与室绝缘，提供旋转接触，以使在覆层过程中可将一偏电压加在基底上。
真空室被抽气至压力约5×10-3毫巴，加热至约150℃。
然后已镀过的龙头经受高偏压等离子弧清洗，其中一负偏压约500伏加到已镀的龙头上，同时约500安培的电弧被冲击并维持在阴极上。清洗持续的时间近五分钟。
氩气以足以使压力维持在约3×10-2毫巴的速度被引入。3分钟内平均厚度约0.000004英寸的锆层沉积在镀铬的龙头上。阴极弧沉积法包括，加直流电到阴极以获得一约500安培的电流，引氩气到室中使室内压力保持在约1×10-2毫巴，如上面描述的那样以行星形式旋转龙头。
锆层沉积以后，把夹心层加到锆层上。将氮气周期地引入真空室中，同时持续约500安培的电弧放电。氮气的速度以脉冲的形式改变，即周期地从足以使到达基底的锆原子充分反应形成氮化锆的最大流量，至0值或不足以与全部锆原子完全反应的某一低值之间改变。氮气流脉冲持续的时间为1到2分钟(30秒到1分钟供氮，然后停止)。整个脉冲沉积时间约15分钟，产生了一个10到15层的夹心叠层，其中每层的厚度约0.0000015英寸。在夹心层中的沉积材料在充分反应的氮化锆和锆金属(或含氮极少的亚化学计算的ZrN)间交替。
夹心层沉积以后，氮流量保持最大值(足以形成充分反应的氮化锆)，持续时间5到10分钟，以在夹心层上形成一个厚的“彩色层”。这个氮化锆层沉积以后，引入约0.1标准升/分的额外的氧气流达30秒到1分钟，氮气和氩气的流量保持在其前值。形成了混合的反应产物的薄层(氧氮化锆)，其厚度约0.0000002到0.0000005英寸。在最后的沉积阶段结束时，熄灭电弧，打开真空室，取出带有覆层的基底。
尽管为了说明，本发明的某些实施方案已被描述，但应该明确，在本发明的总的范围内，可以有不同的实施方案和修改方案。

Claims (30)

1.其表面至少部分有覆层的制品，该覆层包括：
至少一层由镍组成的层；
铬组成的层；
锆、钛或锆钛合金组成的层；
由锆化合物、钛化合物或锆钛合金化合物，和锆、钛或锆钛合金所组成的多个交替层构成夹心层；
由锆化合物、钛化合物或锆钛合金化合物组成的层；和
由氧化锆、氧化钛或锆钛合金氧化物组成的层。
2.权利要求1的制品，其中所述的由锆化合物、钛化合物或锆钛合金化合物组成的层是由锆化合物组成的。
3.权利要求1的制品，其中所述的由锆、钛或锆钛合金组成的层是由锆组成的。
4.权利要求3的制品，其中所述的由锆化合物、钛化合物或锆钛合金化合物组成的层是由锆化合物组成的。
5.权利要求4的制品，其中所述的由锆化合物组成的层是由氮化锆组成的。
6.权利要求5的制品，其中所述的由氧化锆、氧化钛或锆钛合金氧化物组成的层是由氧化锆组成的。
7.权利要求2的制品，其中所述的由氧化锆、氧化钛或锆钛合金氧化物组成的层是由氧化锆组成的。
8.权利要求6的制品，其中所述的至少一层由镍组成的层是由一层镍组成的层所组成的。
9.权利要求1的制品，其中所述的至少一层由镍组成的层是由一层镍组成的层所组成的。
10.权利要求6的制品，其中所述的至少一层由镍组成的层是由两层不同的镍组成的层所组成的。
11.权利要求10的制品，其中所述的镍组成的层中之一是由半光亮镍组成的。
12.权利要求11制品，其中另一个所述的镍组成的层是由光亮镍组成的。
13.权利要求1的制品，其中所述的至少一个镍层是由两个不同的镍层组成的。
14.权利要求13的制品，其中所述的镍组成的层之一是由半光亮镍组成的。
15.权利要求14的制品，其中另一个所述的镍组成的层是由光亮镍组成的。
16.其至少部分表面有覆层的制品，该覆层包括：
至少一层由镍组成的层；
由铬组成的层；
由锆、钛或锆钛合金组成的层；
由锆化合物、钛化合物或锆钛合金化合物，和锆、钛或锆钛合金组成的许多交替层构成的夹心层；和
由锆化合物、钛化合物组成的层；及由锆、钛或锆钛合金，与氧和/或氮的反应产物组成的层。
17.权利要求16的制品，其中所述的由锆、钛或锆钛合金组成的层是由锆组成的。
18.权利要求17的制品，其中所述的由锆化合物、钛化合物或锆钛合金化合物组成的层是由锆化合物组成的。
19.权利要求18的制品，其中所述的由锆、钛或锆钛合金，与氧和/或氮的反应产物组成的层是由锆、氧和氮的反应产物组成的。
20.其至少部分表面有覆层的制品，该覆层包括：
由半光亮镍组成的层；
由光亮镍组成的层；
由铬组成的层；
由锆、钛或锆钛合金组成的层；
由氮化锆、氮化钛或锆钛合金氮化物，和锆、钛或锆钛合金组成的许多交替层构成的夹心层；和
由氮化锆、氮化钛或锆钛合金氮化物组成的层；和由氧化锆、氧化钛或锆钛合金氧化物组成的层。
21.权利要求20的制品，其中所述的由锆、钛或锆钛合金组成的层是由锆组成的。
22.权利要求21的制品，其中所述的由氮化锆、氮化钛或锆钛合金氮化物组成的层是由氮化锆组成的。
23.权利要求22的制品，其中所述的由氧化锆、氧化钛或锆钛合金氧化物组成的层是由氧化锆组成的。
24.其至少部分表面有覆层的制品，该覆层包括：
由半光亮镍层组成的层；
由光亮镍层组成的层；
由铬组成的层；
由锆、钛或锆钛合金组成的层；
由氮化锆、氮化钛或锆钛合金氮化物，和锆、钛或锆钛合金组成的许多交替层构成的夹心层；
由氮化锆、氮化钛或锆钛合金氮化物组成的层；和
由锆、钛或锆钛合金，与氧和/或氮的反应产物组成的层。
25.权利要求24的制品，其中所述的由钛、锆或锆钛合金组成的层是由锆组成的。
26.权利要求25的制品，其中所述的由氮化锆、氮化钛或锆钛合金氮化物组成的层是由氮化锆组成的。
27.权利要求25的制品，其中所述的由锆、钛或锆钛合金，与氧和/或氮的反应产物组成的层是由锆、氧和氮的反应产物组成的。
28.其至少部分表面有覆层的制品，该覆层包括：
由锆、钛或锆钛合金组成的层；
由锆化合物、钛化合物或锆钛合金化合物，和锆、钛或锆钛合金组成的许多交替层构成的夹心层；
由锆化合物、钛化合物或锆钛合金化合物组成的层；和
由锆、钛或锆钛合金，与氧和/或氮的反应产物组成。
29.权利要求28的制品，其中所述的由锆化合物、钛化合物或锆钛合金化合物组成的层是由锆化合物组成的。
30.权利要求28的制品，其中所述的由锆、钛或锆钛合金组成的层是由锆组成的。
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