CN1161495C - 带有覆层的制品 - Google Patents

带有覆层的制品 Download PDF

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CN1161495C
CN1161495C CNB981096980A CN98109698A CN1161495C CN 1161495 C CN1161495 C CN 1161495C CN B981096980 A CNB981096980 A CN B981096980A CN 98109698 A CN98109698 A CN 98109698A CN 1161495 C CN1161495 C CN 1161495C
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layer
zirconium
inch
titanium
nickel
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CN1208085A (zh
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R・W・苏格
R·W·苏格
威尔特
R·P·威尔特
穆森三世
S·R·穆森三世
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Masco Corp
Musco 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
    • C23C28/40—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
    • 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
    • C23C14/06—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
    • 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
    • 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
    • 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
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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
    • 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
    • C23C28/34—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
    • 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
    • C23C28/34—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
    • 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
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • 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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    • Y10T428/12583—Component contains compound of adjacent metal
    • 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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    • 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

一种制品，其表面有多层覆层，它包括：沉积在制品表面的至少一层镍层，沉积在镍层上的钯镍合金层，沉积在钯镍合金层上的一个难熔金属、更好是锆层，沉积在难熔金属层上的一个由难熔金属化合物层和金属层交替构成的夹心层，沉积在夹心层上的一个难熔金属化合物、最好是氮化镍层，以及沉积在难熔金属化合物层上的一个由难熔金属氧化物组成的层，或难熔金属、氧和氮的反应产物组成的层。该覆层为该制品提供了抛光黄铜的颜色，也为该制品提供了耐磨保护和抗腐蚀保护。

Description

带有覆层的制品
本发明涉及用于基底，特别是黄铜基底的多层装饰性和保护性覆层。
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，然后把一有机物覆层，如丙烯酸衍生物、尿烷、环氧化物等物质组成的覆层涂覆在抛光的表面上。这种方法通常能达到令人满意的效果，但抛光和打磨操作也存在着缺点，特别是当制品的型状复杂时很费劲。而且，已知的有机覆层并不总如希望的那样持久，特别是当用于户外的制品暴露于风雨和紫外线的辐射之中时尤为如此。因此，如果能够为黄铜制品，或者其它金属制品提供一种覆层，它不仅使制品呈现高度抛光的黄铜的外观，还能起到耐磨并防腐蚀的作用，这将是相当有益的。本发明提供了这样的覆层。
本发明的目的在于提供其表面有多层覆层的基底。更确切地说，本发明涉及一种在其表面沉积着特定类型金属或金属化合物的多层迭加涂层的金属基底，特别是的黄铜基底。该覆层有装饰作用并有抗腐蚀和抗磨作用。该涂层提供了高度抛光的黄铜外观。因此，其上带有覆层的制品表面与高度抛光的黄铜制品相仿佛。
直接沉积在基底表面的第一层由镍组成。第一层可以是单一层，或者较好的是由不同的两层如直接沉积在基底表面的半光亮镍层和在半光亮镍层之上的光亮镍层组成。沉积在镍层上的是由钯合金、最好是钯/镍合金组成的层。钯合金层上面一层是由非贵重难熔金属构成的。难熔金属层上是夹心层，它由非贵重难熔金属化合物、如锆的化合物、钛的化合物、铪的化合物或钽的化合物，最好是氮化锆或氮化钛，及非贵重难熔金属、如锆、钛、铪或钽，最好是锆或钛的多层交替组成的。在夹心层上是由非贵重难熔金属化合物、最好是由钛化合物或锆化合物，如氮化锆或氮化钛组成。非贵重难熔金属化合物层上是顶层，它由非贵重难熔金属、最好是锆或钛与氧、氮的反应产物组成。
镍和钯合金层采用电镀法镀覆。难熔金属如锆层、难熔金属化合物如锆的化合物层、以及非贵重难熔金属与氧、氮的反应产物层最好采用气相沉积法如溅射离子沉积法镀覆。
图1是其表面上有多层沉积覆层的部分基底的横截面。
基底12可以是任何可镀的金属或合金基底，如铜、钢、黄铜、钨、镍合金等。在较佳实施方案中基底是黄铜。
用常规的公知的电镀法把镍层13沉积在基底12的表面上。这些方法包括使用常规的公知的电镀液如用Watts液作为镀液。一般这种公知镀液含有溶解在水中的硫酸镍、氯化镍和硼酸。也可以使用所有的公知及市售的氯化物、氨基磺酸盐和氟硼酸盐镀液。这些镀液可以任意地包含一些公知的常规化合物，多数是有机物，来作为均化剂、光亮剂等。为了产生镜面状的亮镍层，将至少一种I级光亮剂和至少一种II级光亮剂加入到电镀溶液中。I级光亮剂是含有硫的有机化合物。II级光亮剂为不含硫的有机化合物。II级光亮剂也能起到均匀化作用，当被加入到不合有含硫的I级光亮剂的镀液中时，会产生半亮的镍沉积物。I级光亮剂包括烷基萘、苯磺酸、苯和萘的二磺酸、三磺酸、苯和萘的磺酰胺、如邻磺酰苯甲酰亚胺之类的磺酰胺、乙烯基和丙烯基磺酰胺和磺酸。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级光亮剂已为本领域普遍技术人员熟知，并在市上可容易得到。它们在美国专利No.4421611中被说明，在此声明将此专利结合在本文中。
镍层13可以是一单层，如由半光亮镍组成或由光亮镍组成的层，或者是一双层，如包括由半光亮镍组成的层和由光亮镍组成的层。镍层的厚度范围通常在约0.0001英寸到约0.0035英寸之间。
如本领域中普通技术人员公知的那样，在镍层沉积在基底表面上以前，将基底浸在常规的和公知的酸活化浴液中，受到酸的活化作用。
如图中所说明的，在一实施方案中，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16层由光亮镍层组成。这个双镍层增强了对基底的防腐蚀保护能力。半光亮的不含硫的层14直接沉积在基底12上。然后，将含半光亮镍层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至少要对防腐保护是有益的。通常，半光亮镍层厚度至少约为0.00005英寸，较好是至少约0.0001英寸，更好是至少约0.00015英寸。厚度的上限通常并不重要，它取决于次要条件如成本。但是，它通常不应超过约0.0015英寸的厚度，较好是不超过约0.001英寸，更好是不超过约0.00075英寸。光亮镍层16的厚度一般至少约为0.00005英寸，较好是至少约0.000125英寸，更好是至少约0.00025英寸。光亮镍层的厚度上限不重要，根据成本等因素确定。但是，厚度通常不超过约0.0025英寸，较好是不超过约0.0002英寸，更好是不超过约0.0015英寸。光亮镍层16也可以起均匀化层的作用，它能覆盖或填充基底上的缺陷。
沉积在光亮镍层16上的是由钯合金组成的层20。钯合金、最好是钯/镍合金层20主要起到减少含难熔金属如锆的层如层22与镍层之间的电耦合作用。
钯/镍合金层20中钯比镍的重量比例是从约50∶50到约95∶5，较好是从约60∶40到约90∶10，最好是从约70∶30到约85∶15。
可以用任何公知的常规沉积方法包括电镀法将钯/镍合金层沉积在镍层上。本领域中普通技术人员对电镀钯的工艺是熟知的。通常这些方法使用钯盐或配合物如钯的氯化胺盐，镍盐如镍的硫酸胺盐，有机光亮剂等。在美国专利4849303，4463660，4416748，4428820，4622110，4552628，4628165，4487665，4491507，4545869和4699697中对电镀钯/镍和钯的方法和镀液作了说明，在此声明将这些专利并入在本文中。
钯合金、最好是钯镍合金层20的厚度是至少能有效地减少含难熔金属如锆的层如22层与镍层16间的电耦合作用的厚度。通常，该厚度是至少约0.000002英寸，较好是至少约0.000005英寸，更好是至少约0.00001英寸。厚度的上限不重要，一般从经济角度考虑。通常该厚度不超过约0.0001英寸，较好是不超过约0.00007英寸，更好是不超过约0.00006英寸。
在钯/镍合金中，钯与镍的重量比例取决于在镀液中钯(以盐形式存在)和镍(以盐形式存在)的浓度。在镀液中钯盐的浓度或相对于镍盐浓度的比例越高，则在钯镍合金中钯的比例越高。
沉积在钯合金、最好是钯/镍合金层20上的是22层，它是由非贵重难熔金属如铪、钽锆或钛、较好是锆或钛、更好是锆组成的。
用常规的公知的技术如真空镀覆、物理气相沉积如离子溅射等把层22沉积在层20上。离子溅射技术和装置在下面的文献中已公开：T.VanVorous的“Planar Magnetron Sputtering；A New Industrial CoatingTechnique”，(Solid State Technology，Dec.1976，pp62-66)；U.Kapacz andSchulz的“Industrial Application of Decorative Coatings-Principle andAdvantages of the Sputter Ion Plating Process”，(Soc.Vac.Coat.，Proc.34thArn.Techn.Conf.，Philadelphia，U.S.A.，1991，48-61)和美国专利No.4162954及No.4591418，上述文献经声明并入本文。
简单的说，在溅射离子沉积法中，将难熔金属如锆靶，即阴极，和基底放在真空室中。室内的空气被抽出以形成室中真空条件。将惰性气体如氩引入室中。气体颗粒被电离并被加速至阴极从而撞出锆原子，然后，被撞出的靶材作为覆层沉积在基底表面。
通常22层的厚度是至少约0.00000025英寸，较好是至少约0.0000005英寸，更好是至少约0.0000001英寸。厚度的上限范围并不重要，它通常取决于对其它因素如成本的考虑。但是，通常不应超过约0.00005英寸的厚度，较好是不超过约0.000015英寸，更好是不超过约0.00001英寸。
本发明的较佳实施方案中，层22由锆组成，用溅射离子镀法沉积。
沉积在层22上的是夹心层26，它由多层非贵重难熔金属化合物层28和非贵重难熔金属层30交替组成。
通常，层26的厚度是从大约0.00005英寸到大约0.000001英寸，较好是从大约0.00004英寸到大约0.000002英寸，更好是从大约0.00003英寸到大约0.000003英寸。
非贵重难熔金属化合物组成了层28，该层包括铪化合物、钽化合物、钛化合物或锆化合物，较好是钛化合物或锆化合物，更好是锆化合物。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。
利用任何常规并公知的反应性真空沉积法、包括反应性离子溅射法来沉积氮化合物。除了室中引入了与沉积的靶材反应的气体物质外，反应性离子溅射法通常类似于离子溅射。因此，在由氮化锆组成层28的情况下，靶材由锆组成，氮气为引入室中的气体物质。
通常，层28的厚度是至少大约0.00000002英寸，较好是至少大约0.0000001英寸，更好是至少大约0.0000005英寸。通常，层28的厚度不超过0.000025英寸，较好的是不超过0.000010英寸，更好是不超过0.000005英寸。
层30在夹心层26中与非贵重难熔金属化合物层28相交替，它由对层22所述的非贵重难熔金属组成。组成层30较好的金属是钛和锆。
层30采用任何常规和公知的沉积法，如溅射离子沉积或镀法沉积。
层30的厚度至少是约0.00000002英寸，较好是约0.0000001英寸，更好约0.0000005英寸。通常，层30的厚度不超过约0.000025英寸，较好是不超过约0.000010英寸，更好是不超过约0.000005英寸。
夹心层26由多个层28和层30交替组成，它主要用于减少薄膜应力、提高整个薄膜强度，提高化学品耐性，重新排列晶格以在整个薄膜伸展范围内减少孔隙和晶界。
在夹心层26中，交替的金属层30和金属氮化物层28的数量对减少压力和提高化学品耐性通常是有效的数量。一般该数量从约50到约2个交替层28，30，较好是从约40个到约4个、更好是从约30个到约6个层28、30。
形成夹心层26的较好方法是，用离子溅射镀法沉积非贵重难熔金属如锆或钛层30，用反应性离子溅射镀法沉积非贵重难熔金属氮化物如氮化锆或氮化钛层28。
在离子溅射电镀过程中，氮气的流量最好在0值(无氮气引入)至需要引入的氮气量之间变化(脉冲)，以在夹心层26中形成许多金属层30和金属氮化物层28的交替层。
层30与层28的厚度比是至少约20/80，较好是约30/70，更好是约40/60。通常该厚度比不超过约80/20，较好是不超过约70/30，更好是不超过约60/40。
沉积在夹心层26之上的是由非贵重难熔金属化合物、最好是难熔金属氮化物、碳化物或碳化物组成的层32。
层32由铪化合物、钽化合物、钛化合物或锆化合物、较好是钛化合物或锆化合物、最好是锆化合物组成。铪化合物、钽化合物、钛化合物和锆化合物选自氮化物、碳化物和碳氮化物。钛化合物选自氮化钛、碳化钛和碳氮化钛，最好是氮化钛。锆化合物选自氮化锆、碳氮化锆和碳化锆，最好是氮化锆。
用任何公知的常规覆镀法或沉积法如真空涂覆法、反应性离子溅射法等，将层32沉积在层26上。
除了引入了与被撞击的靶材反应的反应气体，反应性离子溅射沉积法一般类似于溅射沉积法。因此，在氮化锆组成层32的情况下，靶由锆组成，氮气作为反应气体引入室中。通过控制与锆反应的氮气量，氮化锆的颜色能够被调成类似于不同色调的黄铜的颜色。
层32通常的厚度是至少约0.000002英寸，较好是至少约0.000004英寸，最好是至少约0.0000006英寸。厚度的上限通常不重要，取决于对如成本的考虑。一般厚度不超过约0.00003英寸，较好是不超过约0.000025英寸，更好是不超过约0.000020英寸.
氮化锆是较好的覆层材料，因为它使制品最接近抛光黄铜的外观。
在本发明的实施方案中，如图所示，层34由非贵重难熔金属、含氧气体，如氧及氮的反应产物组成，该层沉积在层32之上。适用于本发明中的金属是能够在合适条件下、比如在由氧或/和氮组成的反应气体的条件下形成金属氧化物、金属氮化物和金属氧氮化物的金属，该金属可以是如钽、铪、锆和钛，较好的是钛和锆，更好是锆。
金属、氧和氮的反应产物通常由金属氧化物、金属氮化物和金属氮氧化物组成。因此，如锆、氧和氮的反应产物通常由氧化锆、氮化锆和氮氧化锆组成。
层34可以用公知的常规沉积技术沉积，这包括纯金属靶的反应性溅射或由氧、氮化物和/或金属组成的混合靶的反应性溅射、反应蒸镀、离子和辅助离子溅射、离子镀、分子的射线取向生长、化学气相沉积，和用以液体形式存在的有机产物母体沉积技术。然而最好是，本发明的金属反应产物用反应性离子溅射法沉积。在最佳的实施方案中，采用了同时引入氧气和氮气的反应性离子溅射法。
这些包括氧化锆和氮化锆的金属氧化物和金属氮化物以及他们的制备和沉积是常规的、公知的并已在美国专利No.5367285公开，在此声明将该公开文献结合在本文中。
在另一实施方案中，代替了由难熔金属、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组成的层34。组成层34的难熔金属氧化物包括，但不限于，氧化铪、氧化钽、氧化锆和氧化钛，较好是氧化钽和氧化锆，更好是氧化锆。这些氧化物和他们的制备是常规的和公知的。
通常，含金属、氧和氮的反应产物或金属氧化物的层34的厚度至少要对提供改进的耐酸性有效。该厚度一般至少是约0.00000005英寸，较好是约0.0000001英寸，更好是约0.00000015英寸。通常金属氮氧化物层的厚度不应超过0.000005英寸，较好是不超过0.000002英寸，最好是不超过0.000001英寸。
为了便于理解本发明，提供了下面的实施例。实施例是例证性的，不限制本发明。
                          实施例1
将门上的黄铜锁眼盖放入常规的恒温清洗液中30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。然后将黄铜锁眼盖放入常规的超声碱性清洗液中6分钟。超声清洗液的PH值在8.9-9.2，温度维持在160-180°F，含有常规公知的皂类、洗涤剂和软絮凝剂等。超声清洗以后，黄铜锁眼盖被漂洗并放到常规的碱性电清洗液中约2分钟。电清洗槽中有一不溶解的浸入式钢阳极，清洗液的温度在约140-180°F，PH值约10.5-11.5，含有普通的常规洗涤剂。然后漂洗锁眼盖两次并放入常规的酸性活化剂溶液中约1分钟。酸性活化剂溶液的PH值约2.0-3.0，温度为室温，含有基于氟化钠的酸式盐。再将锁眼盖漂洗两次并放入半光亮镍镀液中约10分钟。半光亮镍镀液是一种常规的公知镀液，其PH值约4.2-4.6，温度为约130-150°F，含有NiSO4、NiCl2、硼酸和光亮剂。平均厚度约0.00025英寸的半镍层沉积在锁眼盖的表面。
然后将含有半光亮镍层的锁眼盖漂洗两次并放入光亮镍的镀液中约24分钟。通常光亮镍镀液是常规的镀液，温度在约130-150°F，PH值约4.0-4.8，含有NiSO4、NiCl2、硼酸和光亮剂。平均厚度约0.00075英寸的光亮镍层沉积在半光亮镍层上。将镀过半光亮镍和光亮镍的锁眼盖漂洗三次并放入常规的钯/镍镀液中4分钟。钯镍镀液的温度约85-100°F，PH值约7.8-8.5，并采用了一个不溶解的镀铂的铌阳极。镀液中每升含有6-8克的钯(为金属)，2-4克的镍(为金属)，NH4Cl，湿润剂和光亮剂。平均厚度为0.000037英寸的钯镍合金(钯约80％重量，镍约20％重量)沉积在钯层上。钯镍层沉积在锁眼盖上以后经过五次漂洗，包括超声漂洗，然后用热空气干燥。
将经过钯镍电镀的锁眼盖放入溅射离子镀容器中。该容器是不锈钢真空容器，由德国的Leybold A.G.生产。它通常是一圆筒形的箱子，带有一个用来通过泵抽真空的真空室。一个氩气源经调节阀与真空室连接，利用调节阀改变引入室中的氩气流量。另外，两个氮气源经调节阀与真空室连接，利用调节阀改变引入室中的氮气流量。
两对磁控管型的靶组件以空间相隔的关系安装在室中，并与可变的直流电源的负输出端相连。该靶构成阴极，室壁作为阳极与靶阴极相对应。靶材包括锆。
设有托起基底、即锁眼盖的托架，它可挂在该室的顶上，并由变速电机转动，从而在每对磁控靶组件间传送此基底。此托架是导电的并与可变直流电源的负输出端相连。
将镀过的锁眼盖装到溅射离子镀容器中的基底托架上，将真空室抽真空到大约5×10-3毫巴，用辐射电阻加热器加热至约400℃。对靶材溅射清理，以去除其表面污物，通过对阴极施加足以获得约18安培的电流的电能和引入约200标准立方厘米/分的氩气，进行持续约半分钟的溅射清理。溅射清理过程中压力维持在约3×10-3毫巴。
然后，用低压浸蚀方法清洗锁眼盖。低压浸蚀方法持续约5分钟，并包括在锁眼盖上加一负的直流电势，它在一分钟内从约1200伏加到1400伏，和在阴极上加一直流电，以获得约3.6安培的电流。氩气的引入速度在一分钟内从约800增加到约1000标准立方厘米/分，压力维持在约1.1×10-2毫巴。锁眼盖在磁控管组件之间以每分钟一转的速度旋转。然后，将锁眼盖高压浸蚀清洗约15分钟。在高压浸蚀清洗过程中，把氩气引入真空室中，引入速度在10分钟内从500增到650标准立方厘米/分(例如，开始的流速是500sccm，十分钟以后流速是650sccm，并在高压浸蚀清洗的剩余时间内保持在650sccm)，压力为2×10-1毫巴，将在十分钟内从约1400增加到2000伏特的负电势加到锁眼盖上。锁眼盖在磁控管组合件之间以每分钟一转的速度旋转。室中的压力保持在约2×10-1毫巴。
然后用另一种低压浸蚀方法清洗锁眼盖约5分钟。在这种低压浸蚀过程中，约1400伏特的负电势加到锁眼盖上，直流电加到阴极上，以得到一约2.6安培的电流，以在五分钟内从约800sccm(每分钟标准立方厘米)增加到约1000sccm的流量将氩气引入真空室。压力维持在约1.1×10-2毫巴，锁眼盖以每分钟一转的速度旋转。
通过加电能到阴极以获得约18安培的电流，以约150sccm的流量引入氩气，压力维持在约3×10-3毫巴，将靶材再次溅射清理约一分钟。
在清理过程中，在锁眼盖和磁控管靶组件之间***屏蔽板，以防止靶材沉积在锁眼盖上。
去除屏蔽板，把平均厚度约0.000003英寸的锆层在四分钟的过程中沉积在锁眼盖的钯/镍层上。溅射沉积过程包括加直流电到阴极，以获得约18安培的电流，将约450sccm的氩气引入真空室，维持室内的压力为约6×10-3毫巴，使锁眼盖的旋转速度为约0.7转/分。
锆层沉积以后，将交替的氮化锆和锆层组成的夹心层沉积在该锆层上。以约250标准立方厘米/分的流量引入氩气。加直流电到阴极，得到约18安培的电流。在基底上加约200伏特的偏压。以约80标准立方厘米/分的初始流量引入氮气。然后将氮的流量减少到零或接近零。氮气的脉冲设定在约50％的作业周期产生。脉冲持续约10分钟从而形成约6层的夹心叠层，每层的厚度平均约0.000001英寸。夹心叠层的平均厚度约0.000006英寸。
在氮化锆和锆的交替夹心层沉积后，平均厚度约0.00001英寸的氮化锆层在20分钟内沉积在夹心叠层上。在此步骤中，调整氮气量，使偏离子电流维持在约6.3×10-11安培。氩气量，直流电，偏电压维持如上。
完成氮化锆层沉积以后，锆、氧和氮的反应产物薄层在30秒内沉积，其平均厚度约0.00000025英寸。在此步骤中，保持以约250标准立方厘米/分的流量引入氩，保持阴极电流约18安培，保持偏压约200伏特，设定氮气流量约80标准立方厘米/分。
尽管为了说明，本发明的一些实施方案已被阐述，但可以理解的是，在本发明的总的范围内本发明还可以有不同的实施方案和修改方案。

Claims (12)

1.在其基底的至少部分表面上有多层覆层的制品，所说覆层包括：
半光亮镍组成的层；
光亮镍组成的层；
钯镍合金组成的层；
锆或钛组成的层；
由锆或钛和锆化合物或钛化合物组成的多层交替层，及
锆化合物或钛化合物组成的层。
2.权利要求1的制品，其中所述的锆或钛组成的层是由锆组成的。
3.权利要求2的制品，其中所述的由锆化合物或钛化合物组成的层是由锆化合物组成的。
4.权利要求3的制品，其中所述的锆化合物组成的层是由氮化锆组成的。
5.权利要求1的制品，其中所述的基底是由黄铜组成的。
6.在其基底的至少部分表面上有多层覆层的制品，所说覆层包括：
半光亮镍组成的层；
光亮镍组成的层；
钯镍合金组成的层；
锆或钛组成的层；
由锆或钛和锆化合物或钛化合物组成的多层交替层所构成的夹心层；
锆化合物或钛化合物组成的层；以及
氧化锆或氧化钛组成的层。
7.权利要求6的制品，其中所述的由锆或钛组成的层是由锆组成的。
8.权利要求7的制品，其中所述的由锆化合物或钛化合物组成的层是由锆化合物组成的。
9.权利要求8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。
10.权利要求9的制品，其中所述的基底是黄铜。
11.权利要求6的制品，其中所述的基底是黄铜。
12.在其基底的至少部分表面上有多层覆层的制品，所说覆层包括：
镍组成的层；
钯镍合金组成的层；
锆或钛组成的层；
由锆或钛和锆化合物或钛化合物组成的多层交替层；以及
锆化合物或钛化合物组成的层。
CNB981096980A 1997-04-30 1998-04-30 带有覆层的制品 Expired - Fee Related CN1161495C (zh)

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KR19980081874A (ko) 1998-11-25
GB2324808A (en) 1998-11-04
EP0875603A1 (en) 1998-11-04
DE69802458D1 (de) 2001-12-20
DE69802458T2 (de) 2002-08-22
FR2762852A1 (fr) 1998-11-06
CN1208085A (zh) 1999-02-17
EP0875603B1 (en) 2001-11-14
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CA2236150C (en) 2001-08-28
GB9809056D0 (en) 1998-06-24

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