CN1222586A - 带有覆层的制品 - Google Patents

带有覆层的制品 Download PDF

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CN1222586A
CN1222586A CN98114888A CN98114888A CN1222586A CN 1222586 A CN1222586 A CN 1222586A CN 98114888 A CN98114888 A CN 98114888A CN 98114888 A CN98114888 A CN 98114888A CN 1222586 A CN1222586 A CN 1222586A
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zirconium
layer
compound
nickel
titanium
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CN1157499C (zh
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R·P·威尔特
J·H·彼特森
P·朱特
C·W·特兰德曼
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Masco Corp
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    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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    • 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
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C14/325—Electric arc evaporation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

用包括铜层、镍层、铬层、难熔金属层,最好是锆层,由难熔金属化合物和难熔金属的交替层构成的夹心层。难熔金属化合物层,最好是氮化锆层、及难熔金属氧化物层或由难熔金属、氧和氮的反应产物所组成的层的多层镀覆的制品。该覆层使该制品产生抛光黄铜的颜色,并产和防刮伤,防腐蚀能力及改善的耐酸性能。

Description

带有覆层的制品
本发明涉及制品，尤其是其上带多层装饰和保护覆层的黄铜或锌制品。
近年来，实际应用各种的黄铜或锌制品，如龙头、龙头把手、门扭、门把、门饰等时，首先将这些制品打磨和抛光到高光亮的程度，然后在这种抛光过的表面上涂保护性的有机涂层，比如由丙烯酸、尿烷、环氧化物等组成的涂层。这种体系的缺点是：打磨和抛光工序是很费工的，若制品的形状复杂则尤为如此。还有，这类已知的有机覆层并不是总象所期望地那样耐久，并易受酸腐蚀的影响。因此，若使黄铜或锌制品，当然还有其它的金属制品具有一种覆层，它使该制品具有精抛黄铜的外观、具有耐磨性和防腐性以及改善了的耐酸性，则是有益的。本发明提供这样一种覆层。
本发明用于一种制品，如塑料、陶瓷或金属的制品，最好是金属制品，在它们的至少部分表面上具有多层覆层。本发明适用于这样一种制品或基底，尤其是不锈钢、铝、黄铜或锌之类的金属制品：在其表面上沉积了特定类型的多个叠层的金属层或金属化合物层。这种覆层是装饰用的，而且还可具有耐腐蚀性能，耐磨性和改善了的耐酸性能。该覆层有精抛黄铜的外观，即，有黄铜的色调。因此其上有这种覆层的制品的表面与精抛的黄铜表面相仿佛。
按照一个实施方案，直接沉积在基底表面上的第一层是由铜构成的。该铜层可以是单一的层或它可包含双铜层，如一个碱性铜层和一个酸性铜层。在此铜层上面的是镍构成的层。该镍层可以是单一的层，或它可以是由两层不同的镍层构成，如由沉积在该铜层表面上的半光亮的镍层和叠加在该半光亮镍层上的光亮的镍层构成。沉积在该镍层上的是含铬层。在该铬层之上的是由非贵重的难熔金属或非贵重的难熔金属合金，如锆、钛、铪、钽、或锆-钛合金，而更好是锆、钛或锆-钛合金构成的层。在该非贵重的难熔金属或金属合金层之上的是由非贵重难熔金属化合物或合金化合物和非贵重难熔金属或合金的多个交替层构成的夹心层。由锆的化合物、钛的化合物、铪的化合物、钽的化合物或锆-钛合金的化合物，更好是钛的化合物、锆的化合物或锆-钛合金的化合物，如氮化锆构成的层沉积在该夹心层之上。在该由锆的化合物，钛的化合物或锆-钛合金的化合物构成的层之上的是一个顶层，它由以下构成(ⅰ)氧化锆、氧化钛或锆-钛合金的氧化物，或(ⅱ)非贵重的难熔金属或金属合金，如锆、钛、锆-钛合金、铪等，氧和氮的反应产物。
铜、镍和铬层最好通过电镀形成。难熔金属、如锆，难熔金属化合物，如锆的化合物及氧化锆、氧化钛或锆-钛合金氧化物的层则通过汽相沉积，如物理汽相沉积或化学汽相沉积形成。
图1是其表面上沉积了多层覆层的部分基底的，不按比例的截面图。
图2是类似于1的，本发明的另一实施方案的，展示双镍层的图。
制品或基底10可由任何可镀材料，如塑料、陶瓷、金属或金属合金构成。在一实施方案中，该材料是可镀金属或金属合金，如铜、钢、黄铜、锌、铝、镍合金等。在一较佳实施方案中，该基底是黄铜或锌。
铜层11用，比如，常规的及众所周知的电镀法沉积在制品10的至少部分表面上。电镀铜的工艺和电镀铜的镀液是本技术领域中常规的熟知的。所述电镀包括酸性铜和碱性铜的电镀。特别是，它们述于美国专利US3,725,220、3,769,179、3,923,613、4,242,181及4,877,450中，它们的公开内容在本文中引用作为参考。
较佳的铜层11选自碱性铜和酸性铜。该铜层可以是单层的，由一种类型的铜如碱性铜11a或酸性铜11b构成的，或它可包含两种不同的铜层，如由碱性铜层11a和酸性铜11b构成的层。
该铜层的厚度范围一般为从至少约百万分之100(0.0001)英寸，较好是至少约百万分之150(0.00015)英寸至约百万分之3500(0.035)英寸，更好是约百万分之2000(0.002)英寸。
当使用由，比如，碱性铜层和酸性铜层构成的双铜层时，碱性铜层的厚度一般为至少约百万分之50(0.00005)英寸，更好是至少约百万分之75(0.000075)英寸。此厚度的上限一般不严格。通常，不应超过约万百分之1500(0.0015)英寸，更好是不超过约百万分之1000(0.001)英寸。酸性铜层的厚度一般为至少约百分分之50(0.0005)英寸，更好是至少约百万分之75(0.00075)英寸。此厚度的上限不严格。通常，不应超过约百万分之1500(0.0015)英寸，更好是不超过约百万分之1000(0.001)英寸。
可用常规的和熟知的电镀工艺将镍层13沉积在铜层11上。这些工艺包括采用常规的电镀液，如watts镀液作电镀液。这类镀液一般含溶于水中的硫酸镍、氯化镍及硼酸。所有的氯化物、氨基磺酸盐和氟硼酸盐电镀溶液也均可使用。这些镀液可任选地包含一些广为人知的和常规使用的化合物，如均化剂，光亮剂等。为产生镜面光亮的镍层，往此电镀溶液中加至少一种Ⅰ级的和至少一种Ⅱ级的光亮剂。Ⅰ级光亮剂是含硫的有机化合物。Ⅱ级光亮剂是不含硫的有机化合物。Ⅱ级光亮剂还引起均化，而且向不含含硫的Ⅰ级光亮剂的电镀液中添加时，会形成半光亮的镍沉积物。这些Ⅰ级光亮剂包括烷基萘和苯磺酸、苯和萘的二和三磺酸、苯和萘的氨磺酰，及诸如邻磺酰苯甲酰亚胺之类的氨磺酰、乙烯基和烯丙基氨磺酰及磺酸。Ⅱ级光亮剂一般是不饱和的有机材料，如，炔醇或烯醇、乙氧基化的和过氧化的炔醇，香豆素和醛类。这些Ⅰ和Ⅱ级光亮剂是本技术领域中的普通技术人员公知的，而且易从市上购得。它们，特别是，述于美国专利US.4,421,611中，此文献经参照被结合于本文中。
此镍层可由单层的，如半光亮镍或光亮镍构成，或它可以是包含两种不同镍层的双层，比如，是一种半光亮镍层和光亮镍层所形成的双层。镍层的厚度范围一般为从约百万分之100(0.000100)英寸，更好是约百万分之150(0.000150)英寸至约百万分之3500(0.0035)英寸。
在图2所示的实施方案中，该镍层13是双镍层，并且是由两种不同的镍层14和16构成的。层14由半光亮镍构成，而层16则由光亮镍构成。这种双层的镍沉积物改善了下层基底的防腐蚀性能。该半光亮的，无硫的镀层14是用常规的电镀方法直接沉积在基底10的表面上的。然后将包含了半光亮镍层14的基底10放在光亮镍镀液中，从而在半光亮镍层14上沉积光亮镍层16。
半光亮镍层及光亮镍层的厚度是对于提供腐蚀防护有效的厚度。通常半光亮镍层的厚度为至少约百万分之50(0.00005)，较好是至少约百万分之100(0.0001)，更好是至少约百万分之150(0.00015)英寸。该厚度的上限一般不严，而且决定于次要的考虑，如成本。但，通常不应超过约百万分之1500(0.0015)，较好是不超过约百万分之1000(0.001)，更好是不超过约百万分之750(0.00075)英寸的厚度。光亮镍层16的厚度一般为至少百万分之50(0.00005)，较好是至少约百万分之125(0.000125)，而更是至少约个百万分之250(0.000025)英寸。光亮镍层的上限厚度不严，而且通常受次要考虑，如成本的控制。但一般来说，不应超过约百万分之2500(0.0025)，较好是不超过约百万分之2000(0.002)，更好是不超过百万分之1500(0.0015)英寸的厚度。光亮镍层16还有趋向于覆盖或填充基底中的缺陷的均化功能。
在镍层13，最好在光亮镍层16之上沉积由铬构成的层21。铬层21可用常规的公知电镀技术沉积在层16上。在Brassard的"DecorativeElectroplating-A process in Transition"(Metal Finishing,pp.105-108,June 1988)；Zaki的"Chromium Plating"(PF Diretory,pp.146-160)；及US4,460,438，4,234,396和4,093,522中，除了各种镀铬的镀液之外，还公开了这些技术，上述所有的文献的内容经参照已结合于本文中。
铬的镀液是公知的和市售的。典型的铬镀液含铬酸或其盐，及催化剂离子例如硫酸盐和氟化物。这些催化剂离子可由硫酸或其盐及氟硅酸提供。该镀液可在约112°-116°F下的温度下作业。一般镀铬约5-9伏时采用约150安/英尺2的电流密度。
铬层的厚度一般为至少约百万分之2(0.000002)，较好是至少约百万分之5(0.000005)而更好是至少均百万分之8(0.000008)英寸。通常，该厚度的上限不严，并且由次要的考虑，如成本确定。但，铬层的厚度一般不应超过百万分之60(0.00006)，较好是不超过约百万分之50(0.00005)而更好是不超过约百万分之40(0.00004)英寸。
在铬层21之上沉积由非贵重的难熔金属或金属合金，如铪、钽、锆、钛或锆-钛合金，较好是由锆、钛或锆-钛合金，而更好是由锆构成的层22。
用常规的和公知的技术将层22沉积在层21上，所述技术包含汽相沉积，如阴极弧蒸镀(CAE)或溅射等。溅射技术和设备，特别是，公开于J.Vossen和W.Kern的"Thin Film Processes Ⅱ"(AcadmicPress,1991)；R.Boxman等人的"Hand-book of Vacuum Arc Science andTechnology"(Noyes Pub.,(1995)；)及US 4,162,954及4,591,418中，上述内容经参照均已结合于本文中。
简言之，按溅射沉积法，将作为阴极的难熔金属靶材(如钛或锆)和基底放在真空室中。室中的空气被抽去，从而在该室中形成真空状态。将惰性气体，如Ar，引入此室。该气体的粒子被离子化，从而向靶材加速，结果撞击出钛或锆原子。这种被撞击出来的靶材料通常作为覆膜沉积在基底上。
按照阴极弧蒸镀，通常使数百安培的电弧撞击金属阴极。如锆或钛的表面。电弧使此阴极材料蒸发，它们随后冷凝在基底上，从而形成覆层。
层22的厚度一般至少约百万分之0.25(0.00000025)，较好是至少约百万分之0.5(0.0000005)，而最好是至少约百万分之1(0.000001)英寸。上限厚度不严，一般取决于次要的考虑，如成本。但，层22的厚度一般不应超过约百万分之50(0.00005)，较好是不超过约百万分之15(0.000015)，更好是不超过约百万分之10(0.000010)英寸。
按照本发明的较佳实施方案，层22由钛、锆、或钛-钛合金，最好是由锆构成，而且采用汽相沉积方法得到，如物理的汽相沉积(溅射沉积，或阴极弧蒸镀沉积)。
难熔金属或难熔金属合金，如锆或锆-钛合金层22上沉积夹心层26，它是由非贵重难熔金属的化合物，或非贵重难熔金属合金化合物层28，与非贵重难熔金属或非贵重难熔金属合金层30的交替构成的。这种结构示于附图1和2中，其中22代表难熔金属或难熔金属合金层，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的化合物层，而30代表非贵重难熔金属层或非贵重难熔金属合金层。
包含非贵重难熔金属及非贵重难熔金属合金的层30包括铪、钽、钛、锆、锆-钛合金、锆-铪合金等，而较好是包括锆、钛或锆-钛合金，而最好是包括锆。
包含非贵重难熔金属化合物及非贵重难熔金属合金化合物的层28包含铪的化合物，钽的化合物、钛的化合物、锆的化合物、或锆-钛合金的化合物，较好是包含钛的化合物，锆的化合物或锆-钛合金的化合物、而最好是包含锆的化合物。这些化合物选自氮化物、碳化物及碳氮化物，而以氮化物为佳。因此，钛的化合物选自氮化钛、碳化钛和碳氮化钛，而以氮化钛为佳。锆的化合物选自氮化锆，碳化锆和碳氮化锆，而以氮化锆为佳。
夹心层26的平均厚度一般为约百万分之2(0.000002)-约百万分之40(0.00004)英寸，较好是约百万分之4(0.000004)-约百万分之35(0.000035)英寸，而更好是约百万分这6(0.000006)-约百万分之30(0.000030)英寸。
层28和30中的每层的厚度为至少约百万分之0.01(0.00000001)，较好是至少约百万分之0.25(0.00000025)，而更好是至少约百万分之0.5(0.0000005)英寸。通常，层28和30不应厚于约百万分之15(0.000015)英寸，较好是不大于约百万分之10(0.00001)英寸，更好是不大于约百万分之5(0.000005)英寸。
形成夹心层26的方法是利用离子溅射或阴极弧蒸镀沉积非贵重难熔金属层30，如锆或钛层，接着通过反应性离子溅射或反应性阴极弧蒸沉积非贵重难熔金属氮化物层28，如氮化锆或氮化钛层。
最好是在汽相沉积过程中，如在反应溅射中，氮气的流量在0(未引入氮，或引入氮不足)到一个理想值之间变化(脉冲式)，以便在夹心层26中形成金属30和金属氮化物28的交替叠层。
夹层26中的难熔金属层30和难熔金属化合物28的交替层的层数一般至少为约2，较好是至少约4，而更好是至少约6。一般来说，夹心层26中的难熔金属30和难熔金属化合物28的交替层的数目不应超过约50，较好是不超过约40，更好是不超过约30。
在本发明的一实施方案中，如图1和2所示，汽相沉积于夹心层26之上的是由非贵重难熔金属化合物或非贵重难熔金属合金的化合物，较好是由氮化物，碳化物或碳氮化物，而更好是由氮化物构成的层32。
层32由铪的化合物、钽的化合物、钛的化合物、锆-钛合金的化合物或锆的化合物构成，较好是由钛的化合物、锆-钛合金的化合物或锆的化合物构成，而更好是由锆的化合物构成。钛的化合物选自氮化钛、碳化钛及碳氮化钛，而氮化钛是最好的。锆的化合物选自氮化锆、碳氮化锆及碳化锆，而以氮化锆为佳。
层32提供了耐磨和耐擦伤的性能，以及所需的颜色或外观，如抛光黄铜的颜色或外观。通过任何公知的和常规的汽相沉积技术，如反应性溅射和反应性阴弧蒸发将层32沉积在层26上。
反应性阴极弧蒸镀和反应性溅射与普通的溅射和阴极弧蒸镀相似，但不同的是将与被撞击出的靶材料反应的反应气体引入该室中。因此，在以氮化锆为层32的场合下，以锆构成阴极而氮是引入该室的反应气体。通过控制可用来与锆反应的氮量，则可将氮化锆的颜色调得与各种色调的黄铜颜色相似。
层32的厚度至少要对耐刮伤有效。通常。此厚度为至少百万分之0.1(0.0000001)，较好是至少百万分之1(0.000001)，而更好是百万分之2(0.000002)英寸。上限厚度不严，而且取决于次要条件，如成本。一般不应超过约百万分之30(0.00003)英寸的厚度，较好是不超过约百万分之25(0.000025)，更好是不超过约百万分之20(0.000020)英寸的厚度。
氮化锆，由于它提供了最接近抛光黄铜的外观所以是最佳的覆层材料。
在本发明的一实施方案中，由非贵重难熔金属或金属合金，含氧气体，如氧、以及氮的反应产物所构成的层34沉积在层32上。这些可用来实施本发明的金属是那些在适当的条件下，比如在采用由氧和氮组成的反应气体的条件下，能形成金属氮化物和金属氧化物的金属。这些金属，比如，可以是钽、铪、锆、锆-钛合金以及钛、以钛、锆-钛合金和锆为佳，而最好的是锆。
这种金属或金属合金、氧和氮的反应产物一般包括金属或金属合金的氧化物，金属或金属合金的氮化物及金属或金属合金的氧-氮化物。因此，比如，锆、氧和氮的反应产物的就包括氧化锆、氮化锆及氧-氮化锆。这些包括氧化锆和氮化锆的金属氧化物和金属氮化物及其制备和沉积是常规的和公知的，而且，特别是已公开于US.5,367,285中，其公开的内容已经参照结合于本文中。
可采用公知的常规的汽相沉积技术，这包括反应性溅射和阴极弧蒸镀，沉积层34。
在另一实施方案中，替代由难熔金属或难熔金属合金，氧和氮的反应产物构成的层34的是由非贵重难熔金属氧化物或非贵重难熔金属合金的氧化物构成的层。构成层34的难熔金属氧化物及难熔金属合金的氧化物包括，但不限于，氧化铪、氧化钽、氧化锆、氧化钛及锆-钛合金的氧化物，较佳的是氧化钛、氧化锆及锆-钛合金的氧化物，而更好的是氧化锆。这些氧化物及其制备是常规的和公知的。
含有(ⅰ)非贵重难熔金属或非贵重难熔金属合金、氧和氮的反应产物，或(ⅱ)非贵重难熔金属氧化物或非贵重难熔金属合金的氧化物的层34的厚度一般至少要能有效地改善耐酸性能。通常此厚度为至少约百万分之0.05(0.00000005)英寸，较好是约至少百万分之0.1(0.0000001)英寸，而更好是至少约百万分之0.15(0.00000015)英寸。一般，层34的厚度不应大于约百万分之5(0.000005)英寸，较好是不大于约百万分之2(0.000002)英寸，而更好是不大于约百万分之一(0.000001)英寸。
在本发明的另一实施方案中，在至少一层沉积在至少一层铜层上的镍层上施加这种汽相沉积层。此实施方案与上述的图1和2中的实施方案相似，但缺铬层21。因此，在至少在基底的部分表面上沉积了单或双铜层，在此铜层上电镀单或双镍层，在该镍层上汽相沉积非贵重难熔金属层或合金层，及在该非贵重难熔金属或金属合金层上汽相沉积了由非贵重难熔金属化合物或非贵重难熔金属合金的化合物的多个交替层构成的夹心层。在该夹心层上，用汽相沉积，沉积非贵重难熔金属化合物或非贵重难熔金属合金的化合物。在该层之上，汽相沉积由(ⅰ)非贵重难熔金属氧化物或非贵重难熔金属合金的氧化物构成的层，或由(ⅱ)非贵重金属难熔金属，或非贵重难熔金属合金，氧和氮的反应产物所构成的层。
在本发明的另一实施方案中，将该汽相沉积层沉积在至少一层，如经电镀直接施于部分基底表面上的铜层上。该铜层，与前述各实施方案一样，可以是碱性铜、酸性铜，或它可以是由碱性铜层和酸性铜层构成的双铜层。该汽相沉积层与前述各实施方案中的该种层相同，并且包含沉积在该铜层上的非贵重难熔金属或金属合金及沉积在该非贵重难熔金属或金属合金上的由非贵重难熔金属化合物或非贵重难熔金属合金化合物的交替层构成的夹心层。在该夹心层上汽相沉积了由非贵重难熔金属化合物或非贵重难熔金属合金的化合物构成的层。在此层之上是由(ⅰ)非贵重难熔金属氧化物或非贵重难熔金属合金的氧化物构成的层，或(ⅱ)由非贵重难熔金属或金属合金、氧和氮的反应产物构成的层。
为能更容易理解本发明，提供下列实施例。该实施例是说明性的，因而不对本发明构成限制。
实施例1
将黄铜龙头在含有标准的和公知的皂类、洗涤剂、反絮凝剂等的常规的均温清洁剂槽浴液中放置10分钟，该浴液的pH值保持为8.9-9.2，温度保持为145-200°F。然后将此黄铜龙头置于常规的超声波碱性清洁剂浴液中。该超声波清洁剂浴槽液的pH值保持为8.9-9.2，温度保持为约160-180°F，并且它含有常规的和公知的皂类、洗涤剂、反絮凝剂等。超声波清洁后，冲洗此龙头，再将其于常规的碱性电清洁剂浴液中放置约50秒。将该电清洁剂浴液保持为约140-180°F的温度和约10.5-11.5的pH值，而且它含有标准的和常规的洗涤剂。然后冲洗此龙头，再将其置于常规的酸性活化剂浴液中约20秒。此酸性活化剂浴液的pH值为约2.0-3.0，温度为室温，并含氟化钠为基的酸式盐。
然后将此龙头冲洗，再于常规的和标准的酸性铜镀液中放约14分钟。该酸性铜镀液含硫酸铜，硫酸及痕量的氯化物。此镀液保持于约80°F。在此龙头上沉积了平均约百万分之400(0.0004)英寸厚的铜层。
然后冲洗这个具有铜层的龙头，再将其于光亮镍镀液中放置约12分钟。这种光亮镍镀液一般是常规的镀液，其温度保持在约130-150°F，pH值保持在约4.0-4.8，并含有NiSO4、NiCl2，硼酸和光亮剂。在该铜层上沉积了平均厚度约百万分之400英寸的光亮镍层。将此镀了铜和光亮镍的龙头冲洗3次，随后将其置于采用常规镀铬设备的常规的工业生产用六价铬镀液中约7分钟。这种六价铬镀液是常规的和公知的镀液，它含约32盎司/加仑的铬酸。该镀液还含常规的和公知的镀铬添加剂。该镀液的温度保持于112°-116°F，它采用了混合的硫酸盐/氟化物催化剂。铬酸与硫酸盐之比为约200∶1。在光亮镍层的表面上沉积了约百万分之10(0.00001)英寸的铬层。将此龙头在去离子水中彻底冲洗，然后干燥。将此镀了铬的龙头置于阴极弧蒸镀容器中。该容器一般为园柱封闭形，它包含一个适于借助泵抽空的真空室。借助用于改变进入真空室中的Ar流量的调节阀将Ar气源与此真空室相连。此外，借助用于改变进入此室N2流量的调节阀将N2气源与此室相连。
将园柱形的阴极装在此室的中心，并与可变的直流电源的负输出端相连。该电源的正极与室壁相连。阴极材料包括锆。
将经镀覆的龙头装在一些杆上，16根这样的杆装在围绕阴极外侧的环。整个环绕阴极旋转，同时每支杆则绕各自的轴旋转，从而产生所谓的行星式的运动，这样就使多个装在各杆上的龙头均匀地向阴极暴露。该环一般以数rpm的速度旋转，同时环每转一周各杆转数周。各杆与室是电隔离的，并设有可旋转的接点，从而可在镀覆时将偏电压施于基底。
将真空室抽至约5×10-3毫巴的压力，并加热到约150℃。
然后使此经电镀的龙头经受高偏压电弧等离子清理，其中将约500伏的(负)偏电压加在此经电镀的龙头上，同时约500安培的电弧冲击和保持在阴极上。清理时间约5分钟。
以足以保持约3×10-2毫巴压力的流量引入Ar气。在3分钟时间内在此镀铬龙头上沉积平均厚度约百万之4(0.000004)英寸的锆层。这种阴极弧沉积工艺包括向阴极施以直流电，以达到约500安培的电流，同时向该容器引Ar气，以在该容器中保持约1×10-2毫巴的压力，并使此龙头以上述的行星方式转动。
在沉积锆层之后，在其上施以夹心层。周期性地将N2气流引入真空室，同时持续约500安培的电弧放电。N2气流量是脉冲式的，即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等于0的，或不足以使与全部锆充分反应的某一低值作周期性的变更。氮气流的脉冲周期为1-2分钟(30秒-1分钟充N2，然后停止)。脉冲沉积的总的时间为约15分钟，结果形成10-15层，每层厚约百万分之1-1.5英寸夹心堆积层。在夹心层中的沉积材料是完全反应的氮化锆与金属锆(或氮含量很小的亚化学计量的ZrN)间的交替叠层。
沉积了夹心层后，将N2流量于其最大值(足以形成化学计量比的ZrN)保持5-10分钟，以便在夹心层的顶上形成较厚的“彩色层”。此氮化锆层沉积之后，将约每分钟0.1标准升的辅助O2气流引入30秒-1分钟，同时以上述数值保持N2和Ar气流量。形成混合反应产物的薄层(锆的氧-氮化物)，其厚度约为百万分之0.2-0.5英寸。在最后一次沉积期结束时熄灭电弧，打开真空室并取出被镀覆的基底。
虽然出于说明的目的陈述了本发明的一些实施方案，但在本发明的总的范围内还可有各种实施方案及改进是可以理解的。

Claims (35)

1．至少其部分表面上有多层覆层的制品，该覆层包括：
至少一个由铜构成的层；
至少一个由镍构成的层；
由铬构成的层；
由锆、钛或锆-钛合金构成的层；
由锆的化合物、钛的化合物或锆-钛合金的化合物及锆、钛或锆-钛合金构成的多个交替层所组成的夹心层；
由锆的化合物，钛的化合物或锆-钛合金的化合物构成的层；及
由氧化锆、氧化钛或锆-钛合金的氧化物构成的层。
2．权利要求1的制品，其中所述的铜层选自酸性铜和碱性铜。
3．权利要求2的制品，其中所述的铜是碱性铜。
4．权利要求2的制品，其中所述铜是酸性铜。
5．权利要求2的制品，其中所述的至少一个铜层由酸性铜和碱性铜所组成的双铜层构成。
6．权利要求1的制品，其中所述镍选自半光亮镍和光亮镍。
7．权利要求6的制品，其中所述镍是光亮镍。
8．权利要求6的制品，其中所述镍是半光亮镍。
9．权利要求6的制品，其中所述至少一个镍层由半光亮镍和光亮镍所组成的双镍层构成。
10．权利要求1的制品，其中所述锆化合物、钛化合物或锆-钛合金的化合物是氮化锆、氮化钛或锆-钛合金的氮化物。
11．权利要求2的制品，其中所述镍选自半光亮镍和光亮镍。
12．权利要求11的制品，其中所述的镍是半光亮镍。
13．权利要求11的制品，其中所述镍是光亮镍。
14．权利要求11的制品，其中所述至少一个镍层由半光亮镍和光亮镍所组成的双镍层构成。
15．权利要求11的制品，其中所述的锆化合物，钛化合物和锆-钛合金的化合物是氮化锆、锆-钛合金的氮化物，或氮化钛。
16．权利要求14的制品，其中所述的锆化合物，钛化合物，或锆-钛合金的化合物是氮化锆，氮化钛或锆-钛合金的氮化物。
17．权利要求13的制品，其中所述的锆化合物，钛化合物或锆-钛合金的化合物选自氮化锆、氮化钛或锆-钛合金的氮化物。
18．其至少部分表面上有多层覆层的制品，所述覆层包括：
至少一层由铜构成的层；
至少一层由镍构成的层；
铬构成的层；
锆、钛或锆-钛合金构成的层；
由锆化合物、钛化合物或锆-钛合金的化合物及锆、钛或锆-钛合金所组成多个交替层构成的夹心层；
锆化合物、钛化合物或锆-钛合金的化合物构成的层；及
锆、钛或锆-钛合金、氧和氮的反应产物构成的层。
19．权利要求18的制品，其中所述铜选自碱性铜和酸性铜。
20．权利要求19的制品，其中所述铜是碱性铜。
21．权利要求19的制品，其中所述铜是酸性铜。
22．权利要求19的制品，其中所述的至少一个铜层由酸性铜和碱性铜所组成的双铜层构成。
23．权利要求18的制品，其中所述镍选自半光亮镍和光亮镍。
24．权利要求23的制品，其中所述镍是光亮镍。
25．权利要求23的制品，其中所述镍是半光亮镍。
26．权利要求23的制品，其中所述至少一个镍层由半光亮镍和光亮镍所组成的双镍层构成。
27．权利要求18的制品，其中所述的锆化合物、钛化合物或锆-钛合金的化合物是氮化锆、氮化钛或锆-钛合金的氮化物。
28．权利要求19的制品，其中所述镍选自半光亮镍和光亮镍。
29．权利要求28的制品，其中所述镍是半光亮镍。
30．权利要求28的制品，其中所述镍是光亮镍。
31．权利要求28的制品，其中所述的至少一个镍层由光亮镍和半光亮镍所组成的双镍层构成。
32．权利要求28的制品，其中所述的锆化合物、钛化合物、或锆-钛合金化合物是氮化锆、氮化钛或锆-钛合金的氮化物。
33．权利要求18的制品，其中所述的锆化合物、钛化合物或锆-钛合金化合物是锆化合物或锆-钛合金化合物。
34．权利要求33的制品，其中所述锆化合物或锆-钛合金的化合物是锆化合物。
35．权利要求34的制品，其中所述的锆化合物是氮化锆。
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630710A (zh) * 2015-03-16 2015-05-20 广东迪奥应用材料科技有限公司 一种玫瑰金色装饰镀涂层及其制备方法
CN104947108A (zh) * 2015-06-12 2015-09-30 东莞市明谷一纳米材料有限公司 软体离子双面镀膜低电阻的制备方法
CN105908156A (zh) * 2016-07-06 2016-08-31 苏州亚科塑胶有限公司 一种在塑胶表面电镀金色镀层的方法
CN109423646A (zh) * 2017-08-24 2019-03-05 华为技术有限公司 一种复合涂层的制备方法以及电子产品制件

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FR2762856B1 (fr) 2001-03-09
FR2762856A1 (fr) 1998-11-06
GB9809057D0 (en) 1998-06-24
CA2236153A1 (en) 1998-10-30
EP0875600B1 (en) 2001-12-19
JPH10330962A (ja) 1998-12-15
CN1157499C (zh) 2004-07-14
GB2324809B (en) 2002-05-01
EP0875600A1 (en) 1998-11-04
KR19980081878A (ko) 1998-11-25
DE69802996D1 (de) 2002-01-31
GB2324809A (en) 1998-11-04
DE69802996T2 (de) 2002-08-08
US5948548A (en) 1999-09-07
CA2236153C (en) 2002-01-22

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