CN1197996C - 带有覆层的制品 - Google Patents

带有覆层的制品 Download PDF

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CN1197996C
CN1197996C CNB981148875A CN98114887A CN1197996C CN 1197996 C CN1197996 C CN 1197996C CN B981148875 A CNB981148875 A CN B981148875A CN 98114887 A CN98114887 A CN 98114887A CN 1197996 C CN1197996 C CN 1197996C
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layer
compound
alloy
goods
constitutes
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CN1207420A (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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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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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
    • C23C14/34—Sputtering
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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
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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
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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
    • 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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    • 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
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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
    • C23C28/40—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
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    • 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
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    • 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
    • Y10T428/12542—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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    • Y10T428/12535—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
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Abstract

用由Ni层、难熔金属层，较好是Zr层，以难熔金属的化合物和难熔金属组成的多个交替层所构成的夹心层、在该夹心层上的难熔金属化合物层及难熔金属的氧化物层或由难熔金属、O和N的反应产物构成的层所组成的多层覆层镀覆的一种制品。该覆层提供了抗刮伤、防腐蚀和改善了的耐酸性能。

Description

带有覆层的制品
本发明涉及其上有多层的装饰和保护覆层的制品，尤其是黄铜制品。
近年来，实际应用各种黄铜制品，如龙头，龙头把手，门扭、门把、门饰等时，首先将该制品的表面打磨和抛光到高的光亮度，然后在该抛光的表面上施以保护性的有机覆层，如由丙烯酸类物，尿烷，环氧化物等组成的覆层。这种体系的缺点是打磨和抛光作业很费工，若此制品的形状复杂时则尤为如此。还有，这种已知的有机覆层不总是象所期望那样地耐久，因而易受酸的浸蚀。因此，若黄铜制品，当然还有其它制品，无论是塑料、陶瓷或金属制品设有使它们具有精抛黄铜的外观、耐磨性、防腐蚀性及改善了的耐酸性的覆层则是有益的。本发明提供了这样的覆层。
本发明的目的在于这样的制品，比如，塑料、陶瓷，或金属的，特别是金属的制品：在其至少部分表面上沉积了多层的覆层。尤其是，本发明的目的在于其表面上沉积了某些特定类型的金属或金属化合物的多层的叠加金属层的金属制品，如不锈钢、铝，黄铜或锌制品。这种覆层是装饰性的，而且还提供了耐腐蚀，耐磨和改善了的耐酸性能。该覆层提供了精抛黄铜的外观，即具有黄铜的色调。因此，其上有这种覆层的制品表面与精抛黄铜的表面相仿佛。
首先在该制品表面上沉积一层或几层电镀层。然后用汽相沉积法在此电镀层顶上沉积一或几层汽相沉积层。直接沉积在该基底表面上的第一层由镍构成。该第一层可为一单层，或它可由两种不同的镍层构成，如，由直接沉积在该基底表面上的半光亮镍层及叠加在此半光亮镍层上的光亮镍层构成。沉积在该镍层之上的是由非贵重难熔金属或金属合金，如由Zr、Ti、Hf、Ta或Zr-Ti合金，而最好是由Zr、Ti或Zr-Ti合金构成的层。在该难熔金属或难熔金属合金构成的层之上的是夹心层，它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和非贵重难熔金属，或非贵重难熔金属合金的交替层构成的。在夹心层之上的是由非贵重难熔金属化合物或非贵重的难熔金属合金的化合物构成的层。在该非贵重难熔金属化合物或非贵重难熔金属合金的化合物层之上的是由非贵重难熔金属氧化物、非贵重难熔金属合金的氧化物，或非贵重难熔金属或金属合金、氧和氮的反应产物所构成的层。
镍层是用电镀施加的。非贵重金属或非贵重金属合金层、夹心层、非贵重金属化合物或非贵重金属合金的化合物层、及由非贵重难熔金属氧化物、非贵重难熔金属合金的氧化物，或非贵重难熔金属或金属合金、氧和氮的反应产物所构成的层是用汽相沉积，如阴极弧蒸镀或溅射施加的。
图1是其表面上经电镀及汽相沉积沉积了多层覆层的部分基底的，不按比例的截面图。
图2是类似与图1的图，但其镍层由双镍层构成。
制品或基底12可由任何可镀材料，如塑料、陶瓷、金属或金属合金构成。特别是由可镀金属或金属合金，如铜、钢、黄铜、锌、铝、镍合金等构成。在一较佳实施方案中，该基底是黄铜或锌。
按本发明，如于图1和2中所示，将第一层或第一系列层电镀在制品表面上。将第二系列层汽相沉积在该电镀层的表面上。镍层13可用常规的或公知的电镀法沉积在基底12的表面上。这些方法包括采用常规镀液，如Watts镀液作电镀溶液。这类镀液一般含硫酸镍、氯化镍和硼酸的水溶液。所有的氯化物、氨基磺酸盐及氟硼酸盐电镀溶液也都可采用。这些镀液可任选地包括一些已知的和常规使用的化合物，如均化剂或光亮剂等。为了产生镜面光亮的镍层，则向此电镀溶液加至少一种I级光亮剂和至少一种II级光亮剂。I级光亮剂是含S的有机化合物。II级光亮剂是不含S的有机化合物。II级光亮剂还会引起均化，而且当将其加于无含S的I级光亮剂的电镀溶液中时，则形成半光亮镍沉积物。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，苯和萘的磺酰胺和诸如邻磺酰苯甲酰亚胺之类的磺酰胺、乙烯基和炔丙基磺酰胺及磺酸。II级光亮剂一般是不饱和的有机材料，如炔醇或烯醇，乙氧基化和丙氧基化的炔醇，香豆素和醛类。这些I级和II级光亮剂在本技术领域中是公知的，并且易从市上购得。特别是它们被述于US.4,421,611中，其内容经参照已结合于本文中。
该镍层可由单层，如半光亮镍或光亮镍层构成，或它可以是含有两种不同镍层的双层，如包含由半光亮镍构成的层和由光亮镍构成的层。镍层的厚度范围一般为约百万分之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。
如在本技术领域中所公知的那样，在将镍层沉积在基底表面上之前，先将基底置于常规的和已知的酸性浴液中使其经受酸性活化。
在图2所示的一实施方案中，镍层13实际上由两个不同的镍层14和16构成。层14由半光亮镍构成，而层16由光亮镍构成。这种双层的镍沉积改善了对下面基底的防腐蚀保护。半光亮的无S的镀层14是用常规电镀法直接沉积在基底12的表面上的。然后将带有半光亮镍层14的基底12置于光亮镍电镀液中，于是在半光亮镍层14上就沉积了光亮镍层16。
半光亮镍和光亮镍层的厚度是一种能有效地产生改善了的防腐蚀性能的厚度。通常，半光亮镍层的厚度为至少约百万分之50(0.00005)英寸，较好是至少约百分之100(0.0001)英寸，而更好是至少约百万分之150(0.00015)英寸。其上限厚度一般不严格，而且决定于次要条件，如成本。但，该厚度一般不应超过约百万分之1 500(0.0015)英寸，更好是不超过约百分之1000(0.001)英寸，最好是不超过约百万分之750(0.00075)英寸。光亮镍层16的厚度一般为至少约百万分之50(0.00005)英寸，较好是至少约百万分之125(0.000125)英寸，而更好是至少约百万分之250(0.000250)英寸。光亮镍层的上限厚度不严格，一般为次要条件，如成本，所控制。但，该厚度一般不应超过约百万分之2500(0.0025)英寸，较好是不超过约百万分之2000(0.002)英寸，而更好是不超过约百万分之1500(0.0015)英寸。光亮镍层还起着均化层的作用，它倾向于掩盖或填充基底上的缺陷。
在镍层13上所沉积的是由非贵重难熔金属或金属合金，如由Hf、Ta、Zr、Ti或Zr-Ti合金，较好是由Zr、Ti或Zr-Ti合金，而更好是由Zr构成的层22。
层22用常规而公知的技术沉积在层13上，该技术包括汽相沉积，如阴极弧蒸镀(CAE)或溅射等。尤其是在J.Vossen和W.kem的“Thin Film ProcessII”(Academic Press，1991)；R.Boxman等人的“Handbook of Vacuum ArcScience and Technology”(Noyes Pub.，1995)；及US.4,162,954和4,591,418中已公开的溅射技术及设备，其全部公开内容经参照已结合在本文中。
简言之，按溅射沉积法，将作为阴极的难熔金属靶(如Ti或Zr)和基底放在真空室中。室中的空气经抽空，从而在该室中形成真空状态。将惰性气体、如Ar引入此室。气体颗粒经电离，然后向靶加速，结果撞击出Ti或Zr原子。然后被撞击出来的靶材一般作为覆膜沉积在基底上。
在阴极弧蒸镀时，一般为数百安培的电弧冲击金属阴极，如Zr或Ti的表面。电弧将阴极材料蒸发，然后它凝在基底上，从而形成覆层。
层22的厚度一般为至少约百万分之0.25(0.00000025)英寸，更好是至少约百万分之0.5(0.0000005)英寸，而最好是至少约百万分之1(0.000001)英寸。其厚度上限不严格，并且一般取决于次要条件，如成本。但，层22的厚度一般不应大于约百万分之50(0.00005)，较好是不大于约百万分之15(0.000015)，更好是不大于约百万分之10(0.000010)英寸。
在本发明的一个较佳实施方案中，层22由Ti、Zr或Ti-Zr合金构成，较好是由Zr构成，并用溅射或阴极弧蒸镀沉积。
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28和非贵重难熔金属或非贵重难熔金属合金30的交替层构成的夹心层26沉积在难熔金属或难熔金属合金层22，如Zr或Zr-Ti合金层上。附图1和2中展示了这种结构，其中22代表难熔金属或难熔金属合金层，较好是Zr或Zr-Ti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。
层30所包含的非贵重难熔金属和非贵重难熔金属合金包括Hf、Ta、Ti、Zr、Zr-Ti合金、Zr-Hf合金等，较好的是Zr、Ti或Zr-Ti合金，而更好是Zr。
层28所包含的非贵重难熔金属化合物和非贵重难熔金属合金的化合物包括Hf的化合物、Ta的化合物、Ti的化合物、Zr的化合物和Zr-Ti合金的化合物、较好的是Ti的化合物、Zr的化合物或Zr-Ti合金的化合物，而更好的是Zr的化合物。这些化合物选自氮化物、碳化物和碳氮化物，而以氮化物为佳。因此，该Ti的化合物就选自TiN，TiC和碳氮化钛，而以TiN为佳。Zr的化合物就选自ZrN2、ZrC和碳氮化锆，而以ZrN2为佳。
夹心层26的平均厚度一般为约百万分之2(0.000002)英寸-约百万分之40(0.00004)英寸，较好是约百万分之4(0.000004)英寸-约百万分之35(0.000035)英寸，而更好是约百万分之6(0.000006)英寸-约百万分之30(0.00003)英寸。
层28和30的厚度一般各为至少约百万分之0.01(0.00000001)英寸，较好是至少约百万分之0.25(0.00000025)英寸，而更好是至少约百万分之0.5(0.0000005)英寸。一般来说，层28和30的厚度不应大于约百万分之15(0.000015)，较好是不大于约百万分之10(0.00001)，更好是不大于约百万分之5(0.000005)英寸。
形成夹心层26的方法是利用溅射或阴极弧蒸镀，从而沉积非贵重难熔金属，如Zr或Ti的层30，然后通过反应性溅射或阴极弧蒸镀沉积非贵重难熔金属氮化物，如ZrN2或TiN的层28。
在汽相沉积，如反应性溅射过程中，最好改变N2气流量(脉冲式的)，这种改变是在0(不引入，或以减小的值引入N2气)和按照在夹心层26上形成金属30和金属氮化物28的多层交替层所需值引入的氮之间变化。
夹心层26中的难熔金属30和难熔金属化合物28的交替层的层数一般至少约为2，较好是至少约为4，而更好是至少约为6。夹心层26中的难熔金属30和难熔金属化合物28的交替层的层数一般不应超过约50，较好是不超过约40，更好是不超过约30。
在如图1和2所示的本发明的一实施方案中，在夹心层26上所汽相沉积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Hf的化合物、Ta的化合物、Ti的化合物、Zr-Ti合金的化合物。或Zr的化合物，较好地是由Ti的化合物、Zr-Ti合金的化合物或Zr的化合物，而更好是由Zi的化合物构成。钛的化合物选自TiN、TiC和碳氮化钛，而以TiN为佳。Zr的化合物选自ZrN2、ZrC和碳氮化Zr，而以ZrN2为佳。
层32提供耐磨和耐刮伤性能及合乎要求的颜色或外观，如精抛黄铜的颜色和外观。用任何公知的和常规的汽相沉积技术，如反应性溅射和阴极弧蒸镀将层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，但将欲与被撞击的靶材反应的气体引入此室中。因此，在ZrN2为层32的情况下，用Zr构成阴极，而N2是引入该室的反应气体。通过控制可用来与Zr反应的N2量，就可将ZrN2的颜色调节得与各种色调的黄铜的颜色相似。
层32的厚度至少要能有效地提供抗刮伤性。该厚度一般为至少百万分之0.1(0.0000001)英寸，较好是至少百万分之1(0.000001)英寸，而更好是至少百万分之2(0.000002)英寸。该厚度的上限不严格，而且一般决定于次要条件，如成本。一般不应超过约百万分之30(0.00003)英寸，较好是不超过约百万分之25(0.00025)英寸，更好是不超过约百万分之20(0.00002)英寸的厚度。
由于ZrN2能产生最接近精抛黄铜的外观，所以它是优选的覆层材料。
在本发明的一实施方案中，层34由非贵重的耐熔金属或金属合金，含氧气体，如氧气及氮的反应产物构成并沉积在层32上。可用于实施本发明的金属，是那些在适当的条件下能形金属氧化物和金属氮化物的金属，所述的条件，比如是采用由氧和氮构成的反应气体。这类金属，比如，可以是Ta、Hf、Zr、Zr-Ti合金及Ti，Ti、Zr-Ti合金较好，而更好是Zr。
这类金属或金属合金、氧和氮的反应产物一般由该金属或金属合金的氧化物，该金属或金属合金的氮化物及该金属或金属合金的氧-氮化物构成。因此，比如，Zr、O和N的反应产物就包括氧化锆、ZrN2和Zr的氧-氮化物。这类包括氧化锆和ZrN2合金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，尤其是已公开于US，5,367,285中，其公开内容经参照已结合于本文中。
可用公知的和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，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替代了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。构成层34的难熔金属氧化物和难熔金属合金的氧化物包括，但不限于，Hf的氧化物、Ta的氧化物、Zr的氧化物、Ti的氧化物和Zr-Ti合金的氧化物，以Ti的氧化物，Zr的氧化物及Zr-Ti合金的氧化物为好，而更好是Zr的氧化物。这些氧化物及其制备是常规的和公知的。
包括(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。该厚度一般为至少约百万分之0.05(0.00000005)英寸，较好是至少约百万分之0.1(0.0000001)英寸，而更好是至少约百万分之0.15(0.00000015)英寸。层34的厚度一般不应大于百万分之5(0.000005)英寸，较好是不大于约百万分之2(0.000002)英寸，更好是不大于约百万分之1(0.000001)英寸。
为了更容易理解本发明，提供以下的实施例。该实施例是说明性的，因而不构成对本发明的限制。
实施例1
将黄铜龙头在含有标准的和公知的皂类、洗涤剂、反絮凝剂的均热的清洁剂浴液内放约10分钟，其PH值保持为8.9-9.2，温度保持为180-200°F。然后将此黄铜龙头放在常规的超声波碱性清洁剂浴液中。该超声波清洁剂浴液的PH值保持为8.9-9.2，温度为160-180°F，并且含常规的和公知的皂类、洗涤剂、反絮凝剂等。超声波清洗后，冲洗此龙头，然后将其放在常规的碱性电清洗剂浴液中。该电清洗剂浴液的温度保持在约140-180°F，PH值保持为约10.5-11.5，并含标准的和常规的洗涤剂。然后两次冲洗此龙头，再将其放在常规的酸性活化剂浴液中。该酸性活化剂浴液的PH值约为2.0-3.0，温度为室温，并含有以氟化钠为基的酸式盐。然后将此龙头冲洗2次。再将其于光亮镍镀液中放约12分钟。光亮镍镀液一般是常规镀液，其温度保持在130-150°F，PH保持为约4.0，并含有NiSO4，NiCl2、硼酸及光亮剂。在龙头表面上沉积了平均厚度约百万分之400(0.0004)英寸的光亮镍层。用去离子水彻底冲洗此龙头，然后将其干燥。将此镀镍龙头放在阴极弧蒸镀容器中。该容器一般为封闭圆柱形，带有适于用泵抽空的真空室。经用于改变进入该室中的Ar流量的调节阀将Ar气源与该室相连。另外，经用于改变进入该室的N2流量的调节阀将N2气源与该室连通。
将圆柱形的阴极装在该室的中央，并与可变的D.C电源的负输出端相连。该电源的正侧与室壁相连。阴极材料包括Zr。
将镀过的龙头装在一些杆上，将共16根杆装在围绕阴极外侧的环上。整个环绕阴极旋转，而同时每根杆绕其各自轴旋转，从而产生所谓行星式的运动，这使得装在每根杆上的多个龙头向阴极均匀地暴露。该环一般以数rpm的速度旋转，环每转一周而使每根杆转数周。各杆与室电隔离，并设有可转动的触点，以便在镀覆时可将偏压加在基底上。
将真空室抽至约5×10-3毫巴的压力，并加热到约150℃。
然后使该经电镀的龙头经受高偏弧等离子清理，其中对该经电镀的龙头施以约500伏的(负)偏压，同时使约500安培的电弧冲击和保持在阴极上。这种清理的持续时间约为5分钟。
以足以维持3×10-2毫巴压力的流量引入Ar气。在3分钟的时期中，在该镀铬的龙头上沉积平均厚度约百万分之4(0.000004)英寸的Zr层。该阴极弧沉积工艺包括向该阴极施以达到约500安培电流的D.C电，向该容器引入Ar气以在其中保持约1×10-2毫巴的压力，以及使此龙头以上述的行星方式转动。
在沉积了Zr层之后，将夹心层加在此Zr层上。事先将N2气流引入真空室，同时持续约500安培的电弧放电。N2流量是脉冲的，即在从足以使到达基底的Zr原子完全反应而形成ZrN2的最大流量，至等于0，或不足以与全部的Zr完全反应的某一低值的最小流量间作周期性的改变。N2流量脉冲周期为1-2分钟(30秒-1分供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英寸的夹心叠层。在夹心层中，完全反应的Zr的氮化物和金属Zr的沉积材料相互交替(或与含较少量的N的亚化学计算的ZrN交替)。
沉积了夹心层之后，将最大值(足以形成完全反应的ZrN2的值)的N2气流量保持5-10分钟，结果在夹心层顶上形成较厚的“彩色”层。沉积了这层ZrN2层之后，以30秒-1分钟的时间另外引入约0.1标升/分的O2，同时将N2和Ar的流量保持于其各自的前述值。厚度约为百万分之0.2-0.5英寸的混合反应产物(Zr的氧-氮化物)的薄层就形成了。在这最后的沉积期结束时，将电弧熄灭，打开真空室，然后取出经镀覆的基底。
虽然为了说明，陈述了一些实施方案，但可以理解的是，在本发明的范围内还可以有各种的实施方案及改进。

Claims (27)

1、在其至少部分表面上带有覆层的制品，该覆层包括：
至少一层由镍构成的层；
由Zr、Ti或Zr-Ti合金构成的层；
由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物和Zr、Ti或Zr-Ti合金所组成的多个交替层所构成的夹心层；
由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物构成的层；及
由锆的氧化物，钛的氧化物或Zr-Ti合金的氧化物构成的层。
2、权利要求1的制品，其中所述的由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物构成的层是由Zr的化合物构成的。
3、权利要求1的制品，其中所述的Zr、Ti或Zr-Ti合金构成的层是由Zr构成的。
4、权利要求3的制品，其中所述的由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物构成的层是由Zr的化合物构成的。
5、权利要求4的制品，其中所述的由Zr的化合物构成的层是由氮化锆构成的。
6、权利要求5的制品，其中所述的由Zr的氧化物、Ti的氧化物或Zr-Ti合金的氧化物构成的层是由Zr的氧化物构成的。
7、权利要求2的制品，其中所述的由Zr的氧化物、Ti的氧化物或Zr-Ti合金的氧化物构成的层是由Zr的氧化物构成的。
8、权利要求6的制品，其中所述的由Ni构成的至少一个层是由Ni构成的单一层所构成的。
9、权利要求1的制品，其中所述的由Ni构成的至少一个层是由Ni组成的单一层所构成的。
10、权利要求6的制品，其中所述的由Ni构成的至少一个层是由Ni构成的两个不同层所构成的。
11、权利要求10的制品，其中由Ni构成的所述层中的一种是由半光亮Ni构成的。
12、权利要求11的制品，其中由Ni构成的所述层中的第二种是由光亮Ni构成的。
13、权利要求1的制品，其中所述的由Ni构成的至少一个层是由Ni所组成的两个不同层构成的。
14、权利要求13的制品，其中所述的由Ni构成的层的一种是由半光亮Ni所构成的。
15、权利要求14的制品，其中所述的由Ni构成的层中的第二种是由光亮Ni所构成的。
16、在其至少部分表面上带有覆层的制品，该覆层包括：
由Ni构成的至少一个层；
由Zr、Ti、或Zr-Ti合金构成的层；
由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物及Zr、Ti或Zr-Ti合金所组成的多个交替层构成的夹心层；
由Zr的化合物或Ti的化合物构成的层；及
由Zr、Ti或Zr-Ti合金与O和/或N的反应产物构成的层。
17、权利要求16的制品，其中所述的由Zr、Ti或Zr-Ti合金构成的层是由Zr构成的。
18、权利要求17的制品，其中所述的由Zr的化合物、Ti的化合物或Zr-Ti合金的化合物构成的层是由Zr的化合物构成的。
19、权利要求18的制品，其中所述的由Zr、Ti或Zr-Ti合金与O和/或N的反应产物构成的层是由Zr、O和N的反应产物构成的。
20、在其至少部分表面上带有覆层的制品，该覆层包括：
由半光亮Ni构成的层；
由光亮Ni构成的层；
由Zr、Ti或Zr-Ti合金构成的层；
由氮化锆、氮化钛或Zr-Ti合金的氮化物和Zr、Ti或Zr-Ti合金所组成的多个交替层构成的夹心层；
由氮化锆、氮化钛或Zr-Ti合金的氮化物构成的层；
及由氧化锆、氧化钛或Zr-Ti合金的氧化物构成的层。
21、权利要求20的制品，其中所述的由Zr、Ti或Zr-Ti合金构成的层是由Zr构成的。
22、权利要求21的制品，其中所述的由氮化锆、氮化钛或Zr-Ti合金的氮化物构成的层是由氮化锆构成的。
23、权利要求22的制品，其中所述的由氧化锆、氧化钛或Zr-Ti合金的氧化物构成的层是由氧化锆构成的。
24、在其至少部分表面上带有覆层的制品，该覆层包括：
由半光亮Ni构成的层；
由光亮Ni构成的层；
由Zr、Ti或Zr-Ti合金构成的层；
由氮化锆、氮化钛或Zr-Ti合金的氮化物及Zr、Ti或Zr-Ti合金所组成的多个交替层构成的夹心层；
由氮化锆、氮化钛或Zr-Ti合金的氮化物构成的层；及
由Zr、Ti或Zr-Ti合金与O和/或N的反应产物构成的层。
25、权利要求24的制品，其中所述的由Zr、Ti或Zr-Ti合金所构成的层是由Zr构成的。
26、权利要求25的制品，其中所述的由氮化锆、氮化钛或Zr-Ti合金的氮化物构成的层是由氮化锆构成的。
27、权利要求25的制品，其中所述的由Zr、Ti或Zr-Ti合金与O和/或N的反应产物构成的层是由Zr、O和N的反应产物构成的。
CNB981148875A 1997-04-30 1998-04-30 带有覆层的制品 Expired - Fee Related CN1197996C (zh)

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JPH10330963A (ja) 1998-12-15
CN1207420A (zh) 1999-02-10
EP0875599B1 (en) 2001-10-10
KR19980081880A (ko) 1998-11-25
KR100535315B1 (ko) 2006-03-23
US6033790A (en) 2000-03-07
EP0875599A1 (en) 1998-11-04
DE69801950D1 (de) 2001-11-15
DE69801950T2 (de) 2002-07-04
CA2236156C (en) 2001-10-30
GB2324812B (en) 2002-04-24
GB9809061D0 (en) 1998-06-24
GB2324812A (en) 1998-11-04
FR2762858A1 (fr) 1998-11-06
CA2236156A1 (en) 1998-10-30
FR2762858B1 (fr) 2001-03-09

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