CN1198965C - 表面上具有涂层的制品 - Google Patents

表面上具有涂层的制品 Download PDF

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CN1198965C
CN1198965C CNB981024874A CN98102487A CN1198965C CN 1198965 C CN1198965 C CN 1198965C CN B981024874 A CNB981024874 A CN B981024874A CN 98102487 A CN98102487 A CN 98102487A CN 1198965 C CN1198965 C CN 1198965C
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layer
zirconium
palladium
titanium
nickel
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CN1211637A (zh
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R·W·苏格
R·P·威尔特
S·R·穆森三世
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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
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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
    • C23C28/30—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
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    • 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
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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
    • C23C28/30—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
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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
    • C23C28/30—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
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • C23C28/34—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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    • 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
    • C23C28/34—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
    • C23C28/347—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 layers adapted for cutting tools or wear applications
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
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    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other
    • 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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    • Y10T428/12576—Boride, carbide or nitride component
    • 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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    • Y10T428/12611—Oxide-containing component
    • 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

本发明涉及一种镀覆有多层涂层的制品，这些涂层包括沉积在制品表面上的镍层，沉积在镍层上的钯层、沉积在钯层上的钯-镍合金层、沉积在钯-镍合金层上的非贵重耐火金属如锆层、沉积在非贵重耐火金属层上的由非贵重耐火金属化合物如氮化锆和耐火金属如锆的交替层所构成的叠层、沉积在叠层上的非贵重耐火金属化合物如氮化锆层、以及沉积在非贵重耐火金属化合物层上的由非贵重耐火金属氧化物组成的层或由非贵重耐火金属如锆、氧和氮的反应产物所构成的层。

Description

表面上具有涂层的制品
本发明涉及用于制品，特别是黄铜制品的多层保护性涂层。
目前对各种黄铜制品如灯具、三脚架、烛台、门把手和手柄等等的通常处理方法是先将制品表面抛光和细磨到高光泽度，然后再向此已抛光表面涂布一保护性有机涂层，如由丙烯酸、尿烷、环氧树脂等等构成的涂层。虽然这种体系通常令人满意，但是它具有这种缺陷，即抛光和细磨操作，尤其是当制品具有复杂形状的情况下，需花费相当大的劳动。并且，这些公知的有机涂层并不总是如人们希望的那样耐久，特别是在户外应用情况下这些制品是暴露在自然环境和紫外线辐射之中。因此，如果黄铜制品，固然还包括其它金属制品，能够被提供一种既能赋予制品高抛光的黄铜外观，又能提供耐磨性和耐蚀性的涂层，那是相当有利的。本发明提供这样一种涂层。
本发明涉及一种在其表面上设置或沉积多层涂层的金属基体。更具体地，本发明涉及一种金属基体(尤其是黄铜基体)，在其表面上沉积有由某些特定类型的金属或金属化合物构成的多层叠加金属层。此涂层具有装饰性，且又能提供耐蚀性和耐磨性。此涂层提供高度抛光的黄铜外观，也就是说，具有黄铜色调。因此，其上带有此种涂层的制品表面类似于高抛光黄铜表面。
直接沉积在基体表面上的第一层由镍构成。第一层可以是单一的，或者可以由两种不同的镍层组成如由直接沉积在基体表面上的半光亮镍层和叠加在半光亮镍层上的光亮镍层构成。在镍层上设置的是钯层。该钯层比镍层薄。在钯层上是由钯合金，优选是钯/镍合金构成的薄层。在钯合金层上是由非贵重耐火金属如锆、钛、铪或钽，优选是锆和钛所构成的层。在耐火金属层上是由许多非贵重耐火金属，优选为锆或钛，和非贵重耐火金属化合物，优选是锆化合物或钛化合物的交替层所构成的叠层。由锆化合物、钛化合物、铪化合物或钽化合物，优选钛化合物或锆化合物如氮化锆所构成的层设置在该叠层上。由非贵重耐火金属(优选锆或钛)、含氧气体和氮气的反应产物所构成的顶层设置在耐火金属化合物层上。
镍、钯和钯合金层是通过电镀的方法涂覆的。非贵重耐火金属如锆、耐火金属化合物如锆化合物，以及非贵重耐火金属、含氧气体和氮气的反应产物所构成的层通过气相沉积方法如离子溅射沉积法涂覆。
图1是在其表面上沉积有多层涂层的部分基体横截面示意图。
基体12可以是任何可镀覆金属或金属合金基体如铜、钢、黄铜、钨、镍合金和类似金属。在优选实施方案中基体是黄铜。
镍层13采用常规的和熟知的电镀方法沉积在基体12的表面上。这些方法包括使用常规电镀液如瓦特液(Watts bath)作为电镀液。这类镀液通常含有溶于水中的硫酸镍、氯化镍和硼酸。所有氯化物、氨基磺酸盐和氟硼酸盐镀液都可使用。这些镀液还任选地包括一些公知并常用的化合物如整平剂、光亮剂等。为得到特别光亮的镍层要将至少一种选自I类和至少一种选自II类的光亮剂加入到镀液中。I类光亮剂是含硫的有机化合物。II类光亮剂是不含硫的有机化合物。II类光亮剂还可起整平作用，且将其当加入到不含含硫的I类光亮剂的镀液中时会得到半光亮镍沉积层。这些I类光亮剂包括烷基萘和苯磺酸、苯和萘的二磺酸和三磺酸、苯和萘的磺酰胺、以及磺酰胺类如糖精、乙烯基磺酰胺和烯丙基磺酰胺和磺酸。II类光亮剂通常是不饱和的有机物质如炔属醇或烯属醇、乙氧基化炔属醇和丙氧基化炔属醇、香豆素和醛类。这些I类和II类光亮剂是本领域内技术人员所熟知的，且很容易商购到。它们特别记载于美国专利US4,421,611中，该专利在此结合作为参考。
此镍层可以是由诸如半光亮镍或光亮镍构成的单层，还可以是由一层半光亮镍和一层光亮镍层所构成的复合层。此镍层厚度通常在约百万分之100(0.000100)英寸范围内，优选约百万分之150(0.000150)英寸至约百万分之3,500(0.0035)英寸范围内。
正如本领域技术人员所熟知的那样，在该镍层沉积于基体上之前，基体须放置在常规和公知酸液中进行所称的活化作用。
在如图所示的优选实施方案中，镍层13实际上由两种不同的镍层14和16组成。层14由半光亮镍组成，而层16由光亮镍组成。这种复合镍沉积层为下面的基体提供了良好的腐蚀防护。半光亮、无硫层14是采用常规电镀方法直接沉积在基体12的表面上。然后将含有半光亮镍层14的基体12放置在光亮镍镀液中，则光亮镍层16沉积在半光亮镍层14上。
半光亮镍层和光亮镍层的厚度是能够有效的提供良好的腐蚀保护作用的厚度。通常，半光亮镍层的厚度至少是约百万分之50(0.00005)英寸，优选是至少约百万分之100(0.000100)英寸，更优选至少约百万分之150(0.00015)英寸。厚度的上限通常并无严格限制，且一般由次要因素如成本所控制。然而，厚度一般不应当超过约百万分之1,500(0.0015)英寸，优选约百万分之1,000(0.001)英寸，更优选约百万分之750(0.00075)英寸。光亮镍层16的厚度通常为至少约百万分之50(0.00005)英寸，优选为至少约百万分之125(0.000125)英寸，更优选至少约百万分之250(0.000250)英寸。对光亮镍层厚度的上限范围并无严格要求，通常由诸如成本类的条件所控制。然而，厚度一般不应该超过约百万分之2,500(0.0025)英寸，优选约百万分之2000(0.002)英寸，更优选约百万分之1500(0.0015)英寸。光亮镍层16也起到整平层的作用，它趋于覆盖或填充基体中的缺陷。
设置在光亮镍层16上的是一层相当薄的钯层。此钯预镀层18可通过常规和公知的钯电镀技术沉积在层16上。因此，如阳极可以是惰性镀铂钛阳极，而阴极是具有镍层14和16的基体12。钯以钯盐或络合离子形式存在于镀液中。某些络合剂包括诸如记载于US4,486,274中的多胺，这份文献在此结合作为参考。某些其它钯络合剂如在一些电镀方法中用作钯源的钯四胺络合物，记载于美国专利US4,622,110、US4,552,628和US4,628,165中，这些专利在此结合作为参考。某些钯电镀方法记载于美国专利US4,487,665、4,491,507和4,545,869中，这些专利在此结合入本文。
钯预镀层18尤其起到打底层作用以改善钯合金(优选为钯/镍合金层20)与镍层(如图所示实施例中的光亮镍层16)之间的结合力。此钯预镀层18的厚度应至少能够有效地提高钯合金层20与镍层间的结合力。钯预镀层通常的厚度至少为约百万分之0.25(0.00000025)英寸，优选至少约百万分之0.5(0.0000005)英寸，更优选至少为约百万分之一(0.000001)英寸。一般说来，其厚度的上限范围并无严格要求，而是由次要因素如成本所确定。然而，钯预镀层的厚度通常不应当超过约百万分之50(0.00005)英寸，优选为百万分之15(0.000015)英寸，更优选为百万分之10(0.000010)英寸。
钯合金层，优选为钯/镍合金层20尤其起到降低含耐火金属如锆、钛、铪或钽的层22和24与镍层之间的电偶的作用。
钯/镍合金层20中的钯与镍的重量比为约50∶50～约95∶5，优选约60∶40～约90∶10，更优选约70∶30～约85∶15。
该钯/镍合金层可采用公知的和常规的涂层沉积方法(包括电镀方法)沉积在钯预镀层18上。电镀钯方法对于本领域技术人员而言是熟知的。它们通常包括使用钯盐或钯配合物如氯化亚钯胺盐、镍盐如硫酸镍胺、有机光亮剂等等。一些电镀钯/镍的方法和镀液的具体实例记载于美国专利US4,849,303、4,463,660、4,416,748、4,428,820和4,699,697中，这些专利在此都结合入本文。
在钯/镍合金中钯与镍的重量比与在镀液中钯(以其盐的形式)和镍(以其盐形式)的浓度十分相关。在镀液中相对于镍盐浓度如果钯盐浓度或比例越高，则在钯/镍合金中钯的比例就越高。
钯/镍合金层20的厚度是至少能够有效地降低含有铪、钽、锆或钛，优选含有锆或钛，更优选为含锆的镀层和镍层16之间电偶作用的厚度。这一厚度通常至少为约百万分之二(0.000002)英寸，优选至少为约百万分之五(0.000005)英寸，更优选至少为约百万分之十(0.00001)英寸。厚度的上限范围并无严格要求，并通常取决于经济方面的考虑。厚度通常不应当超过约百万分之百(0.0001)英寸，优选为约百万分之70(0.00007)英寸，更优选为约百万分之60(0.00006)英寸。
设置在钯合金，优选为钯/镍合金层20之上的是由非贵重耐火金属如铪、钽、锆或钛，优选为锆或钛，更优选为锆所组成的层22。
涂层22是采用常规和公知技术如真空涂覆法、物理气相沉积如离子溅射等技术沉积在层20上的。离子溅射技术和设备公开在T.Van Vorous著的“Planar Magnetron Sputtering；新工业涂覆技术”，固态工艺，1976年12月，pp62-66；U.Kapacz和S.Schulz的“装饰性涂层的工业应用途-离子溅射镀覆方法的原则和优点”，Soc.Vac.Coat.，Proc.34thAm.Tech.Conf.，Philadelphia，U.S.A，1991，48-61；以及美国专利US4,162,954和US4,591,418中，这些文献在此结合入本文作为参考。
简要地说，在离子溅射沉积方法中，将耐火金属如钛或锆靶作为阴极并且将基体放置在真空室中。在室内的空气被抽空以在室内产生真空条件。将一种惰性气体如氩气引入真空室中。气体颗粒被离子化后，朝向靶方向加速以撞击钛或锆原子。接着，受撞击的靶材通常以涂膜形式沉积在基体上。
层22的厚度通常至少为约百万分之0.25(0.00000025)英寸，优选至少为约百万分之0.5(0.0000005)英寸，更优选至少为约百万分之一(0.000001)英寸。厚度上限范围并不严格要求，且通常取决于如成本因素。然而，层22的厚度通常应该不厚于约百万分之五十(0.00005)英寸，优选为约百万分之十五(0.000015)英寸，更优选为约百万分之十0.000010英寸。
在本发明的优选实施方案中，层22由钛或锆、优选锆组成，且通过离子溅射镀覆法沉积。
设置在层22上的是由非贵重耐火金属化合物和非贵重金属组成的交替层28和30构成的叠层26。
层26的厚度通常在约百万分之五十(0.00005)～约百万分之一(0.000001)英寸范围内，优选为约百万分之40(0.00004)～约百万分之二(0.000002)英寸范围内，更优选为约百万分之30(0.00003)～百万分之三(0.000003)英寸范围。
非贵重耐火金属化合物层28包括铪化合物、钽化合物、钛化合物或锆化合物，优选为钛化合物或锆化合物，更优选为锆化合物。这些化合物选自氮化物、碳化物和碳氮化物，其中氮化物是优选的。进而，钛化合物选自氮化钛、碳化钛和碳氮化钛，其中氮化钛是优选的。锆化合物选自氮化锆、碳化锆和碳氮化锆，其中氮化锆是优选的。
该氮化物可采用任何常规和公知的反应性真空沉积方法(包括反应性离子溅射方法)进行沉积。反应性离子溅射法大体上类似于离子溅射法，所不同的是能与受撞击的靶材进行反应的气态物质被引入室内。因此，在形成氮化锆层28的情况下，靶由锆构成，而氮气是引入到室内的气态物质。
层28的厚度通常至少为约百万分之200(0.00000002)英寸，优选至少约百万分之0.1(0.0000001)英寸，更优选为约百万分之0.5(0.0000005)英寸。层28的厚度一般不应超过约百万分之二十五(0.000025)英寸，优选为约百万分之十(0.000010)英寸，更优选为约百万分之五(0.000005)英寸。
在叠层26中与非贵重耐火金属化合物层28交替的层30由诸如所述层22的非贵重耐火金属材料构成。构成层30的金属优选是钛和锆。
层30可采用任何常规和公知的气相沉积方法如离子溅射沉积法或电镀法进行沉积。
层30的厚度至少为约百万分之0.02(0.00000002)英寸，优选至少为约百万分之0.1(0.0000001)英寸，更优选至少为约百万分之0.5(0.0000005)英寸。层30的厚度通常不应该超过约百万分之二十五(0.000025)英寸，优选为约百万分之十(0.000010)英寸，更优选为约百万分之五(0.000005)英寸。
在叠层26中的金属层30和金属氮化物层28的交替层的数量通常是达到能够有效地减少应力和提高耐化学性的数目。这一数目一般是约50～约2，优选为约40-约4层28、30，更优选为约30～约6层28、30。
由多层交替层28和30构成的叠层26特别起到减少膜应力、提高整个膜硬度、改善耐化学性和重新排列晶格以减少穿过整个膜表面上的孔隙和晶界的作用。
形成叠层26的优选方法是采用离子溅射方法沉积由非贵重耐火金属如锆和钛构成的层30，接着用反应性离子溅射镀覆法沉积由非贵重耐火金属氮化物如氮化锆或氮化钛构成的层28。
在离子溅射镀覆期间，氮气流速优选地在零(氮气未引入)到以指定值引入氮气的范围之间变化(脉冲式)以形成叠层26中的金属层30和金属氮化物层28的多个交替层28、30。
层30与层28的厚度比至少为约20/80，优选为30/70，更优选为40/60。通常，该值不应该高于80/20，优选70/30，更优选60/40。
设置在叠层26上面的是由非贵重耐火金属化合物，优选为非贵重耐火金属氮化物、碳氮化物或碳化物，以及更优选为氮化物所构成的层32。
层32是由铪化合物、钛化合物、钛化合物或锆化合物，优选钛化合物或锆化合物，更优选锆化合物组成。钛化合物选自氮化钛、碳化钛和碳氮化钛，其中氮化钛是优选的。锆化合物选自氮化锆、碳氮化锆和碳化锆，其中氮化锆是优选的。
层32提供耐磨损性和所需色彩或外观，比如抛光黄铜。层32可通过公知的和常规镀覆或沉积方法如真空涂覆法、反应性离子溅射镀覆法等等沉积在层26上。优选方法是反应性离子溅射镀覆法。
层32的厚度应至少应有效地保证耐磨性。通常该厚度至少为百万分之二(0.000002)英寸，优选至少百万分之4(0.000004)英寸，更优选至少百万分之六(0.000006)英寸。厚度上限通常并无严格要求，且取决于如成本因素。厚度一般不应该超过约百万分之三十(0.00003)英寸，优选约百万分之二十五(0.000025)英寸，更优选约百万分之二十(0.000020)英寸。
氮化钽是优选的涂层材料，因为它能提供最接近于抛光黄铜的外观。在反应性离子溅射过程中，通过控制引入到反应容器中的氮气量，可将氮化钛的颜色做得与各种色调的黄铜颜色类似。
在本发明的一种实施方案中，由非贵重耐火金属、含氮气体如氧气，和氮气的反应产物所组成的层34沉积到层32上。那些可用于本发明实践中的金属是那些在适宜条件下(例如使用由氧气和氮气组成的反应气体)能够形成金属氧化物和金属氮化物的。这些金属可以是如钽、铪、锆和钛，优选钛和锆，更优选锆。
金属、氧气和氮气的反应产物通常由金属氧化物、金属氮化物和金属氧氮化物构成。因此，如锆、氧气和氮气的反应产物通常包括氧化锆、氮化锆和氧氮化锆。
层34可采用公知和常规沉积技术沉积，包括反应性溅射纯金属靶或氧化物、氮化物和/或金属的复合物靶、反应气相沉积、离子和离子加速喷镀、离子镀覆、分子束晶体取向生长、化学气相沉积和从液态有机前体中沉积。然而，优选地，本发明的金属反应产物是通过反应性离子溅射法沉积。在优选实施方案中，反应性离子溅射采用同时引入的氧气和氮气。
这些金属氧化物、金属氧氮化物和金属氮化物(包括氧化锆和氮化锆合金)及其制备与沉积方法都是常规和公知的，这些内容公开在美国专利US5,367,285中，在此结合入本文作为参考。
在本发明的另一个实施方案中，代替层34的是耐火金属、氧气和氮气的反应产物，它是由非贵重耐火金属氧化物组成。构成层34的耐火金属氧化物包括(但不限于此)氧化铪、氧化钽、氧化锆和氧化钛，优选氧化钛和氧化锆、更优选氧化锆。这些氧化物及其制备方法是常规和公知的。
含有金属、氧气和氮气的反应产物或金属氧化物的层34的厚度通常应至少能有效地提供良好的耐酸性。一般，这一厚度至少为约亿万分之五(0.00000005)英寸，优选至少约百万分之0.1(0.0000001)英寸。更优选至少约百万分之0.15(0.00000015)英寸。通常层34的厚度不超过约百万分之五(0.000005)英寸，优选约百万分之二(0.000002)英寸，更优选约百万分之一(0.000001)英寸。
为了更详细地理解本发明，提供下面实施例。该实施例是举例性的，但并不对本发明构成限制。
                          实施例1
将黄铜铭牌放置在含有标准的和公知的肥皂、洗涤剂、反絮凝剂等的常规浸泡清洗剂液中，并将该溶液在pH值为8.9～9.2，且温度为180～200°F下保持30分钟。接着，再将黄铜铭牌在常规d超声波碱性清洗液中放置6分钟。该超声波清洗液的pH值为8.9～9.2，温度维持在约160～180°F范围，且含有常规和公知的肥皂、洗涤剂、反絮凝剂等等。经超声波清洗后，再将铭牌漂洗并在常规碱性电清洗液中放置约2分钟。此电清洗液含有不溶性浸入式不锈钢阳极，保持温度在约140～180°F，pH值约10.5～11.5，且含标准和常规的洗涤剂。之后，再将此铭牌漂洗二次并在常规酸性活化液中放置约1分钟。此酸性活化液的pH值为约2.0～3.0，处于室温，并且含有基于氟化钠的酸式盐。接着再将铭牌漂洗二次，在半光亮镀镍液中放置约10分钟。此半光亮镍镀液是常规和公知镀液，PH值约为4.2-4.6，温度维持在约130～150°F，其中含有NiSO4、NiCl2、硼酸和光亮剂。平均厚度约为百万分之250(0.00025)英寸的半光亮镍层沉积在铭牌表面上。
接着，再将具有半光亮镍层的铭牌漂洗二次且在光亮镍镀液中放置约24分钟。此光亮镍镀液一般是常规镀液，将温度维持在约130～150°F，PH值约4.0～4.8，且含有NiSO4、NiCl2、硼酸和光亮剂。这样平均厚度约百万分之750(0.00075)英寸的光亮镍层沉积在半光亮镍层上。将镀覆有半光亮和光亮镍的铭牌漂洗三次，并于常规钯镀液中放置约1.5分钟。钯镀液采用一不溶性镀铂铌阳极，且温度维持在约95～140°F，PH值约3.7～4.5，并含有约1～5克/升钯(以金属计)和约50～100克/升NaCl。这样平均厚度约为百万分之三(0.000003)的钯层沉积在光亮镍层上。之后将镀钯铭牌漂洗二次。
漂洗后，将涂覆有钯铭的牌在常规钯/镍镀液中放置约4分钟。将钯镍镀液的温度保持在约85～100°F，PH值约7.8～8.5，且采用一不溶性镀铂铌阳极。此镀液含约6～8克/升钯(以金属计)、2～4克/升镍(以金属计)、NH4Cl、润湿剂和光亮剂。这样具有平均厚度约百万分之37(0.000037)英寸的钯/镍合金(约80％重的钯和20％重量的镍)就沉积在钯层上。在沉积钯/镍层之后，将铭牌经过五次漂洗，包括一次超声波清洗，并用热空气干燥。
将镀覆钯/镍的铭牌放在离子溅射镀覆容器中。此容器是由德国的LeyboldA.G生产的不锈钢真空容器。此容器通常是圆柱状腔，内设有适于由泵抽真空的真空室。氩气源通过可以改变氩气流入室中速度的调节阀通到真空室。另外，两股氮气源通过用以改变氮气流入室中速度的调节阀连通到真空室。
两对磁控管型靶组件以一定间隔安装在室内，并连接到可调直流电源的负输出端上。靶作为阴极，而室壁是为靶阴极所共有的阳极。靶材含锆。
安装一承载基体如铭牌的基体托架，例如，它可悬挂在室的顶部，并由可调速电机转动以在每对磁控管靶组件之间传送基体。此托架是导电的，并电连接到可调直流电源的负输出端。
已镀覆的铭牌安装在离子溅射镀覆容器内的基体托架上。将真空室抽空到压力为约5×10-3毫巴，且通过辐射电阻加热器加热到约400℃。靶材经溅射清洁除去表面污物。溅射清洁在下述条件下进行约1.5分钟：向阴极供应足以达到电流约18安培的电能，并以每分钟约200标准立方厘米的速度供入氩气。在溅射清洁过程中压力维持在约3×10-3毫巴。
然后，采用低压浸蚀方法清洗铭牌。此低压浸蚀过程进行约5分钟，包括向铭牌施加负D.C电位(该电位在1分钟时间内从约1200伏提高到约1400伏)，且向阴极供应D.C电能以达到约3.6安培的电流。氩气以在1分钟时间内从每分钟约800标准立方厘米提高到约1000标准立方厘米的速度供入到室内，且压力维持在约1.1×10-2毫巴。铭牌以1转/分钟的速度在磁控管靶组件之间转动。然后对铭牌进行高压浸蚀清洗过程约15分钟。在高压浸蚀过程中，氩气以在10分钟内从每分钟约500标准立方厘米提高到每分钟约650标准立方厘米的速度引入(即，开始阶段，流速为500sccm，10分钟后，流速为650sccm，且在以后的高压清洗过程中保持500sccm。)，压力维持在约2×10-1毫巴，以及将负电位施加给此铭牌，该负电位在10分钟内从约1400伏提高到2000伏。铭牌以1转/分钟的速度在磁控靶组件之间转动。容器内的压力维持在约2×10-1毫巴。
然后，对此铭牌进行约5分钟的另一次低压浸蚀清洗过程。在此低压浸蚀清洗过程中，将约1400伏的负电位施加给此铭牌，将D.C电能供给阴极使电流达到约2.6安培，而氩气以在5分钟时间内由约800sccm(标准立方厘米/每分钟)提高到约1000sccm的速率引入到真空室中。压力维持在约1.1×10-2毫巴，而铭牌以约1rpm的速度转动。
通过将电能供给阴极使电流足够达到约18安培，氩气以约150sccm的速率引入，并将压力维持在约3×10-3毫巴的条件下，对靶材再次溅射清洁约1分钟。
在清洁期间，屏蔽安插在铭牌和磁控管靶组件之间以防止靶材沉积到铭牌上。
移走屏蔽，在四分钟时间内，平均厚度约百万分之三(0.000003)英寸的锆层沉积在铭牌的钯/镍层上。这种溅射沉积方法包括将D.C电源施加给阴极，以达到约18安培的电流，以约450sccm的速度将氩气引入容器，维持容器内压力约6×10-3毫巴，以及以0.7转/分的速度转动铭牌。
在沉积锆层后，再将交替的氮化锆层和锆层的叠层沉积到锆层上。氩气以约250sccm的速度引入真空室，将D.C电源施加给阴极达到约18安培的电流。将约200伏偏置电压施给基体。氮气以初速度约80sccm引入。然后，再将氮气流速降低到零或接近零。这种脉冲氮气设定成以约50％暂载率发生。脉冲过程连续进行约10分钟，产生具有约每层平均厚度约为百万分之一(0.000001)英寸的共约六层的叠层组。此叠层组的平均厚度约为百万分之六(0.000006)英寸。
继由氮化锆和锆构成的交替层的叠层之后，在约20分钟期间内，将具有平均厚度约百万分之十(0.00001)英寸的氮化锆层沉积在叠层组上。在此步骤中，调节氮气以保持局部离子流约为6.3×10-11安培。氩气、D.C电源和偏置电压保持与上面相同。
在沉积氮化锆层完成之后，在约30秒期间内，沉积一层由锆、氧气和氮气的反应产物构成的薄层，该薄层的平均厚度约为百万分之0.25(0.00000025)英寸。在此步骤中，引入氮气的速度保持在250sccm，阴极电流保持在约18安培，偏压保持在约200伏，而氮气流设定在约80sccm。氧气以约20sccm的速度引入。
尽管出于举例说明目的记载了一些本发明的具体方案，但是应当理解到在本发明的整体范围内可以有各种实施方案和各种变化。

Claims (11)

1、一种带有基体的制品，在其至少一部分表面上设置有多层涂层，包括：
由半光亮镍构成的层；
由光亮镍构成的层；
由钯构成的层；
由钯/镍合金构成的层；
由锆或钛构成的层；
由多组由锆或钛层和锆化合物或钛化合物层组成的交替层所构成的叠层；
以及
由锆或钛的化合物构成的层。
2、权利要求1的制品，其中所述由锆或钛构成的层是由锆构成的。
3、权利要求2的制品，其中所述由锆化合物或钛化合物构成的层是由锆化合物构成的。
4、权利要求3的制品，其中所述锆化合物是由氮化锆组成的。
5、权利要求1的制品，其中所述基体是由黄铜组成的。
6、一种带有基体的制品，在其至少一部分表面具有多层涂层，包括：
由半光亮镍构成的层；
由光亮镍构成的层；
由钯构成的层；
由钯/镍合金构成的层；
由锆或钛构成的层；
由多组由锆或钛层和锆化合物或钛化合物层组成的交替层所构成的叠层；
由锆化合物或钛化合物构成的层；以及
由氧化锆或氧化钛构成的层。
7、权利要求6的制品，其中所述由锆或钛构成的层是由锆构成的。
8、权利要求7的制品，其中所述由锆化合物或钛化合物构成的层由锆化合物构成。
9、权利要求8的制品，其中所述锆化合物是氮化锆。
10、权利要求9的制品，其中所述基体是黄铜。
11、权利要求6的制品，其中所述基体是黄铜。
CNB981024874A 1997-04-30 1998-04-30 表面上具有涂层的制品 Expired - Fee Related CN1198965C (zh)

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DE69800654D1 (de) 2001-05-10
GB9809062D0 (en) 1998-06-24
GB2324813B (en) 2002-05-01
GB2324813A (en) 1998-11-04
US5952111A (en) 1999-09-14
CA2236145C (en) 2001-08-21
KR19980081876A (ko) 1998-11-25
FR2762854B1 (fr) 1999-10-08
JPH10324977A (ja) 1998-12-08
EP0875601B1 (en) 2001-04-04
CN1211637A (zh) 1999-03-24
FR2762854A1 (fr) 1998-11-06
EP0875601A1 (en) 1998-11-04
CA2236145A1 (en) 1998-10-30
DE69800654T2 (de) 2001-11-29

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