CN1032702C - 镀有金色渐变交替层的部件及其制备方法 - Google Patents

镀有金色渐变交替层的部件及其制备方法 Download PDF

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CN1032702C
CN1032702C CN 93120347 CN93120347A CN1032702C CN 1032702 C CN1032702 C CN 1032702C CN 93120347 CN93120347 CN 93120347 CN 93120347 A CN93120347 A CN 93120347A CN 1032702 C CN1032702 C CN 1032702C
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tin
gradual change
coating
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CN1089665A (zh
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王殿儒
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GREATWALL TI METALLIC TECHNOLOGY COOPERATIVE DEVELOPMENT Co
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641Nitrides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

本发明涉及一种镀有金色渐变交替层的部件及其制备方法,该方法是在圆形真空室的外壁,沿圆周分布四组阴极电弧源和磁控溅射源,其中三组为Ti或Ti合金,另一组为Au或Au合金。镀件在真空室内沿圆周公转的同时自转,公转与自转的比例为1∶2~3。镀膜过程中首先开启Ti源。并向真空室内通入N2气,当TiN层达到要求厚度后,同时开启Ti源和Au源,镀制渐变交替层。部件由基体和镀层组成,镀层由TiN层、渐变交替层和Au层组成。

Description

镀有金色渐变交替层的部件及其制备方法
本发明涉及一种装饰用的镀有金色渐变交替层的部件及其制备方法,属离子镀技术领域。
金色外部装饰品多年来是采用镀金层,其缺点是镀金层不耐磨。为了维持使用寿命,要求镀金层厚度超过10微米。70年代以来,采用物理气相沉积技术(PVD)镀制的氮化钛(TiN)仿金层获得实际应用。TiN是一种超硬材料,耐磨性能好、抗蚀性能好,其镀层厚度可降到0.5微米,其缺点是色调不如真金美砚。在TiN的表面再镀一薄层Au,可使装饰部件呈现真金的色泽,但金镀层逐步磨去后,会露出底层的TiN,造成两种色调的强烈反差,使装饰品显得破旧。解决问题的途径是在TiN层与镀金层之间增加一种中间层。美国专利US4252862发明的一种镀层是在TiN层与表面镀金层之间加一合金层作为中间层,该TiN合金层是TiN与包括Au等29种元素中的至少一种元素组成的合金。这种镀层的优点是色调优于TiN层,而耐磨优于镀金层。缺点是表面镀金层磨去后,装饰效果变差。
本发明的目的是制备一种镀有金色交替渐变层的部件,使部件在使用过程中,表面的镀金层逐渐磨去后,还会不断出现交替层内的镀金层,以保持装饰物的装饰效果长久不变。
本发明的内容是:金色渐变交替镀层部件由基体和镀层组成。镀层一共有三层,第一层即紧接基体层的是TiN或TiN合金层,第二层是渐变交替层,第三层是Au或Au合金层。镀层也可以是四层,第一层是Ti或Ti合金层,第二层是TiN或TiN合金层,第三层是渐变交替层,第四层为Au或Au合金层。上述镀层中的渐变交替层中含有四种不同物相构成的薄层:a、第一种是纯TiN层,或以Ti为主,含有选自Zr、Al、C、O中的一种以上的元素组成的化合物相。b、第二种是TiN·(Au)层,即以TiN为主,含有Au,或含有Au和选自Zr、Al、C、O、Cu、Ni中的一种以上的元素组成的化合物相。c、第三种是TiN(Au)层,即以Au为主,含有Ti、N,或含有Ti、N和选自Zr、Al、C、O、Cu、Ni中的一种以上的元素组成的金属相。d、第四种是纯Au层,或以Au为主,含有选自Cu、Ni中的一种以上的元素组成的金属相。上述四种物相薄层在交替层中各含有一层以上,薄层之间的成份是渐变的。
制备上述金色渐变交替镀层部件的方法是在圆形真空室的外壁沿圆周均匀分布有产生镀膜气相的阴极电弧源和磁控溅射源。镀膜源共有四组,每组数量不限。其中有三组装的是纯Ti或Ti与Zr、Al中的一种或二种构成的合金,有一组装的是纯Au或Au与Cu、Ni中的一种或二种构成的合金。镀件置于真空室内,沿圆形轨道公转。公转一周的同时,镀件自转二周以上。公转与自转的比例为1∶2~3。镀复时,向真空室内通入N2气,在部件上镀TiN,当TiN层达到要求的厚度后,同时开启四组镀膜源,镀制渐变交替层。
附图说明:
图1是本发明一个实施例的镀制过程示意图。
图2是该实施例中对应于图1中A点的渐变交替层的组成示意图。
下面结合实施例,进一步介绍发明内容。图1中,11是被镀部件的自转轨道,图中的A点是被镀工件上的一点。12是真空室,13是部件在真空室内的公转轨道。图1和图2中的1~6分别表示部件在真空室中公转和自转的不同位置和相对应的渐变交替层中的物相组成。图中a、b、c、d的含义已于上文说明,是表明渐变交替层中各薄层的物相。
实施例1
在圆形真空室内沿圆周均匀分布有四个镀膜源,其中三个为纯Ti,一个为纯Δu。首先开启Ti源,并向真空室内通入N2气,在部件上镀TiN。当TiN层达到要求的厚度,例如0.5微米以后,即同时开启Ti源和Au源,镀制渐变交替层。部件的公转与自转之比为1∶3,部件上A点(如图1所示)由图示位置开始转动,则所得的渐变交替层是一种结构和成份最简单的渐变交替层,只含有Ti、N、和Au这三种元素。图2是部件公转2周,即部件自转6周所得渐变交替层的成分分布图,图中一共出现6个含Au峰。镀完渐变交替层之后,关闭Ti源,最后在部件表面镀一薄层纯Au。
实施例2:
四个镀膜源中,三个为Ti、Al合金靶,一个为Au、Cu合金靶,通入N2气,部件的公转与自转之比为1∶3。所得的渐变交替层中除Ti、N、Au外,还含有Al和Cu,这使部件的外观色泽与实施例1相比,具有另一种不同的格调,可满足不同消费者的需求。
本发明的渐变交替镀层部件在耐磨和色调上都优于TiN与Au组成的单一合金层。交替层中的TiN是超硬材料,它与柔软的Au或Au合金交替相间、钢柔相济,是耐磨材料的一种理想的结构。就色调而言,这种交替层中含有的纯金层,使其色调接近纯金。纯Au层与纯TiN之间的成分渐变可加强两者之间的结合力。

Claims (2)

1、一种镀有金色渐变交替层的部件的制造方法,该方法是在圆形真空室的外壁,沿圆周均匀分布产生镀膜气相的阴极电弧源和磁控溅射源,镀件置于真空室内,其特征在于镀膜源共有四组,其中三组镀膜源装的是纯Ti或Ti与Zr、Al中的一种或二种构成的合金,另一组镀膜源装的是纯Au或Au与Cu、Ni中的一种或二种构成的合金;所述的镀件在真空室沿圆周公转的同时自转,公转与自转的比例为1∶2~3;镀膜过程为首先开启Ti源,并向真空室内通入N2气,当TiN层达到要求厚度后,同时开启Ti源和Au源,镀制渐变交替层。
2、一种用如权利要求1所述的方法制备的镀有金色渐变交替层的部件,由基体和镀层组成,其特征在于所述镀层中紧接基体的第一层为TiN或TiN合金层,第二层为渐变交替层,第三层为Au或Au合金层,所述的渐变交替层中含有以下四种不同物相:
a、第一种是纯TiN层,或以TiN为主,含有选自Zr、Al中的一种以上的元素组成的化合物相;
b、第二种是TiN(Au)层,即以TiN为主,含有Au或含有Au和选自Zr、Al、Cu、Ni中的一种以上的元素组成的化合物相;
c、第三种是Au(TiN)层,即以Au为主,含有Ti、N或含有Ti、N和选自Zr、Al、Cu、Ni中的一种以上的元素组成的金属相;
d、第四种是纯Au层,或以Au为主,含有选自Cu、Ni中一种以上的元素组成的金属相;
上述四种物相在薄层交替层中各有一层以上,薄层之间的成份是渐变的。
CN 93120347 1993-12-04 1993-12-04 镀有金色渐变交替层的部件及其制备方法 Expired - Fee Related CN1032702C (zh)

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CN 93120347 CN1032702C (zh) 1993-12-04 1993-12-04 镀有金色渐变交替层的部件及其制备方法
GB9400237A GB2284431B (en) 1993-12-04 1994-01-07 Golden colored part with layered surface structure

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TW360716B (en) 1993-02-19 1999-06-11 Citizen Watch Co Ltd Golden decorative part and process for producing the same
GB2313606A (en) * 1996-06-01 1997-12-03 Sharp Kk Forming a compound semiconductor film
DE19832571A1 (de) * 1998-07-20 2000-01-27 Hauzer Ind Bv Mehrlagenschicht und Verfahren zu deren Herstellung
KR100768176B1 (ko) 2001-02-07 2007-10-17 삼성에스디아이 주식회사 광학적 전기적 특성을 지닌 기능성 박막
US7026057B2 (en) * 2002-01-23 2006-04-11 Moen Incorporated Corrosion and abrasion resistant decorative coating
JP5281578B2 (ja) 2007-09-19 2013-09-04 シチズンホールディングス株式会社 装飾部品
CN102453873B (zh) * 2010-10-26 2014-07-30 宝鸡市嘉诚稀有金属材料有限公司 一种钛靶材及其制造方法
CN102534488A (zh) * 2010-12-30 2012-07-04 鸿富锦精密工业(深圳)有限公司 具有硬质涂层的被覆件及其制备方法
CN107313013A (zh) * 2017-06-22 2017-11-03 维达力实业(深圳)有限公司 复合镀金薄膜及其制备方法
CN108546925A (zh) * 2018-05-29 2018-09-18 佛山科学技术学院 一种在金属表面制备的玫瑰金薄膜及其制备方法

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US4252862A (en) * 1977-06-10 1981-02-24 Nobuo Nishida Externally ornamental golden colored part
JPS58153776A (ja) * 1982-03-05 1983-09-12 Citizen Watch Co Ltd 装飾部品の製造方法およびそれに用いるイオンプレ−テイング装置

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