CN109136844A - 一种玫瑰金镀层及其制备工艺 - Google Patents

一种玫瑰金镀层及其制备工艺 Download PDF

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CN109136844A
CN109136844A CN201811194919.3A CN201811194919A CN109136844A CN 109136844 A CN109136844 A CN 109136844A CN 201811194919 A CN201811194919 A CN 201811194919A CN 109136844 A CN109136844 A CN 109136844A
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metallic matrix
gold plate
rose gold
rose
target
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杨富国
陈文静
周鉴
张洪华
陈育茹
李旭涛
温薛鑫
丁晨锦
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Foshan University
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Abstract

本发明公开了一种玫瑰金镀层及其制备工艺，所述玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，玫瑰金镀层与金属基体之间有TiCN、Ti和Ni过渡层，以减小残余应力，增加了玫瑰金镀层与金属基体之间的结合强度；该玫瑰金镀层具有良好的耐磨性，同时与金属基体具有较高的结合强度，外表为玫瑰色，不变色，不含铬，从而可以提高铜表带、表壳的使用寿命，并且制备工艺简单快捷，减少了常规电镀工艺给操作工人以及环境所带来的危害，给电镀作业带来了极大的便利。

Description

一种玫瑰金镀层及其制备工艺
技术领域
本发明属于中频磁控溅射镀膜的技术领域，尤其涉及一种玫瑰金镀层及其制备工艺。
背景技术
目前现有很多钟表、手机、首饰等五金件的表面采用电镀的方式，在手机、手表的外壳上真空镀一层金。
在饰品用合金系列中，玫瑰金因色泽华丽典雅，成为风行于当今国内外钟表、首饰行业的潮流时尚。电镀玫瑰金色镀层亦受到广大消费者的喜爱。但目前具有玫瑰金镀层的电镀产品都是将技术零件浸入到电镀液中，利用电解的原理将导电体铺上一层电镀层。但是此种工艺会产生大量含有强酸、强碱、重金属铬的电镀废水，对工人身体伤害很大，而且容易污染地表水和地下水，属于重污染行业；并且常规电镀容易导致涂层厚度不均匀，影响外观效果。另外，现在也有用真空镀的工艺来镀玫瑰金镀层，但这种工艺需经钝化处理，现在钝化处理一般是浸重铬酸钾溶液，重铬酸钾溶液对环境污染较大，不适合大规模应用。
发明内容
本发明提供一种玫瑰金薄镀层及其制备工艺，所述玫瑰金镀层与基体的结合强度高，并且制备工艺简单，减少了常规电镀工艺给操作工人以及环境所带来的危害，给电镀作业带来了极大的便利。
为解决上述目的，本发明采用下述技术方案。
一种玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，所述过渡层包括TiCN层、Ti层和Ni层。
进一步地，所述过渡层从上到下依次为TiCN层、Ti层和Ni层，TiCN层玫瑰金镀层贴合，Ni层与金属基体贴合。
一种玫瑰金镀层的制备工艺，包括以下步骤：
(1)前处理：将金属基体表面打磨抛光后，依次放入酒精和丙酮中超声清洗10～15min；
(2)化学镀镍：将清洗后的金属基体放入化学镀镍液中进行化学镀镍处理，其中化学镀镍液温度为80～92℃、pH值为8～10，化学镀镍处理10min结束后，将金属基体放入流动的去离子水中进行清洗处理，清洗时间15s以上，放入真空干燥箱中充分干燥后迅速放入镀膜机真空室准备下一步处理，其中镀膜机真空室本底真空度为5.0×10-3Pa～8.0×10-3Pa，加热至200～300℃，保温时间20～30min；
(3)离子清洗：向镀膜机真空室通入Ar气，其压力为0.2Pa，开启偏压电源，电压260V，占空比78，辉光放电清洗20～30min；偏压降低至190V，开启离子源离子清洗20～30min，然后开启电弧源Ti靶，偏压200～300V，靶电流65A，离子轰击Ti靶5～6min；
(4)沉积Ti：调整Ar气压至0.4～0.45Pa，偏压降低至50～60V，电弧镀Ti5～7min；
(5)沉积TiCN：调整工作气压为0.32～0.36Pa，偏压58V，Ti靶电流50～60A；开启N2，调整N2流量为50sccm，开启C2H2，调整C2H2流量为50sccm，沉积温度为120～200℃，中频磁控溅射沉积TiCN40～50min；
(6)沉积玫瑰金镀层：关闭Ti靶材，关闭N2，关闭C2H2；调整Ar气压至0.9～1.8Pa，偏压至100～200V，开启金靶电源，电流调制5～6A，中频磁控溅射沉积玫瑰金10～20min；
(7)后处理：关闭金靶电源，关闭偏压电源、离子源及气体源，保温20～25min，镀层结束；
(8)钝化处理：将镀有玫瑰金镀层的金属基体浸金银保护水，温度为30℃,钝化处理5min，取出烘干。
进一步地，在化学镀镍的步骤中，其化学镀镍液的配比为：硫酸镍30～40g/L，次磷酸钠20～30g/L，氯化镍20～30g/L，苹果酸铵20～30g/L，钼酸钠5ppm。
本发明的有益效果为：一种玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，玫瑰金镀层与金属基体之间有TiCN、Ti和Ni过渡层，以减小残余应力，增加了玫瑰金镀层与金属基体之间的结合强度；该玫瑰金镀层具有良好的耐磨性，同时与金属基体具有较高的结合强度，外表为玫瑰色，不变色，不含铬，从而可以提高铜表带、表壳的使用寿命；其中过渡层的TiCN层为单相Na-Cl型结构，呈现(111)择优取向的柱状晶，并且TiCN层具有C元素，因此TiCN层的硬度和抗氧化温度都得到了提高，此外，TiCN层可以和Ti层、Ni层形成多层膜结构，不但可以保持良好的结合强度，还能提高涂层的韧性；另一方面，其制备过程简单快捷，减少了常规电镀工艺给操作工人以及环境所带来的危害，给电镀作业带来了极大的便利。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，所述过渡层包括TiCN层、Ti层和Ni层。
进一步地，所述过渡层从上到下依次为TiCN层、Ti层和Ni层，TiCN层玫瑰金镀层贴合，Ni层与金属基体贴合，由于此金属基体为Cu，Cu硬度较低，而TiCN层硬度高，因此Cu与TiCN层直接结合，则易会使得应力分布不均匀，且残余应力大，直接影响成品质量，而在Cu表面镀Ni可以提高Cu的表面硬度，使得金属基体与TiCN层的硬度差别不大，从而减小残余应力，提高成品质量。
一种玫瑰金镀层的制备工艺，包括以下步骤：
(1)前处理：将金属基体表面打磨抛光后，依次放入酒精和丙酮中超声清洗10～15min；
(2)化学镀镍：将清洗后的金属基体放入化学镀镍液中进行化学镀镍处理，其中化学镀镍液温度为90℃、pH值为9，化学镀镍处理10min结束后，将金属基体放入流动的去离子水中进行清洗处理，清洗时间15s以上，放入真空干燥箱中充分干燥后迅速放入镀膜机真空室准备下一步处理，其中镀膜机真空室本底真空度为5.0×10-3PaPa，加热至220℃，保温时间25min；
(3)离子清洗：向镀膜机真空室通入Ar气，其压力为0.2Pa，开启偏压电源，电压260V，占空比78，辉光放电清洗25min；偏压降低至190V，开启离子源离子清洗24min，然后开启电弧源Ti靶，偏压230V，靶电流65A，离子轰击Ti靶6min；
(4)沉积Ti：调整Ar气压至0.43Pa，偏压降低至55V，电弧镀Ti6min；
(5)沉积TiCN：调整Ar气压为0.33Pa，偏压58V，Ti靶电流50A；开启N2，调整N2流量为50sccm，开启C2H2，调整C2H2流量为50sccm，沉积温度为140℃，中频磁控溅射沉积TiCN50min；
(6)沉积玫瑰金镀层：关闭Ti靶材，关闭N2，关闭C2H2；调整Ar气压至1.4Pa，偏压至150V，开启金靶电源，电流调制5A，中频磁控溅射沉积玫瑰金20min；
(7)后处理：关闭金靶电源，关闭偏压电源、离子源及气体源，保温25min，镀层结束；
(8)钝化处理：将镀有玫瑰金镀层的金属基体浸金银保护水，温度为30℃,钝化处理5min，取出烘干。
进一步地，在化学镀镍的步骤中，其化学镀镍液的配比为：硫酸镍45g/L，次磷酸钠25g/L，氯化镍25g/L，苹果酸铵27g/L，钼酸钠5ppm。
对照例1
一种玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间不具有过渡层。
上述玫瑰金属镀层的制备方法，包括下述步骤：
(1)前处理：将金属基体表面打磨抛光后，依次放入酒精和丙酮中超声清洗10～15min；
(2)沉积玫瑰金镀层：将步骤(1)清洗好的金属基体放入镀膜机真空室，调整Ar气压至1.4Pa，偏压至150V，开启金靶电源，电流调制5A，中频磁控溅射沉积玫瑰金20min；
(3)后处理：关闭金靶电源，关闭偏压电源、离子源及气体源，保温25min，镀层结束；
(4)钝化处理：将镀有玫瑰金镀层的金属基体浸金银保护水，温度为30℃,钝化处理5min，取出烘干。
对照例2
一种玫瑰金镀层，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，其过渡层为TiCN层和Ti层，其中TiCN层与玫瑰金镀层贴合，Ti层与金属基体贴合。
上述玫瑰金镀层的制备工艺为以下所述：
(1)前处理：将金属基体表面打磨抛光后，依次放入酒精和丙酮中超声清洗10～15min；
(2)沉积Ti：将步骤(1)清洗好的金属基体放入真空镀膜室，并调整Ar气压至0.43Pa，偏压降低至55V，电弧镀Ti6min；
(3)沉积TiCN：调整Ar气压为0.33Pa，偏压58V，Ti靶电流50A；开启N2，调整N2流量为50sccm，开启C2H2，调整C2H2流量为50sccm，沉积温度为140℃，中频磁控溅射沉积TiCN50min；
(4)沉积玫瑰金镀层：关闭Ti靶材，关闭N2，关闭C2H2；调整Ar气压至1.4Pa，偏压至150V，开启金靶电源，电流调制5A，中频磁控溅射沉积玫瑰金20min；
(5)后处理：关闭金靶电源，关闭偏压电源、离子源及气体源，保温25min，镀层结束；
(6)钝化处理：将镀有玫瑰金镀层的金属基体浸金银保护水，温度为30℃,钝化处理5min，取出烘干。
将实施例1、对照例1及对照例2制得的玫瑰金镀层按热震法进行测试，将测试样品加热到250℃，保温30min后立即放入常温冷水中骤冷，发现实施例1中的镀层无气泡、片状剥落等与基体分离现象，这说明基体与镀层结合良好；对照例1中的镀层产生若干小气泡，这说明对照例1中的镀层已与基体分离，对照例2中的镀层出现裂纹，但无气泡产生，这说明镀层与基体结合良好，但内部残余应力大，使得镀层出现裂纹。
将实施例1、对照例1及对照例2制得玫瑰金镀层进行磨损试验，试验环境温度为室温，湿度为RH60～65％，在摩擦系数为0.37的钢板上进行滑动，滑动时间为3min，滑行距离100m；从磨痕形貌SEM图中测得，实施例1中的磨痕宽度≦300μm、对照例1中的磨痕宽度≧800μm、对照例2中的磨痕宽度≧500μm，这说明实施例1中的镀层具有良好的耐磨性。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种玫瑰金镀层，其特征在于，包括金属基体，所述金属基体为铜，金属基体的表面为玫瑰金镀层，在玫瑰金镀层与金属基体之间具有过渡层，所述过渡层包括TiCN层、Ti层和Ni层。
2.根据权利要求1所述的一种玫瑰金镀层，其特征在于，所述过渡层从上到下依次为TiCN层、Ti层和Ni层，TiCN层玫瑰金镀层贴合，Ni层与金属基体贴合与。
3.一种玫瑰金镀层的制备工艺，其特征在于，包括以下步骤：
(1)前处理：将金属基体表面打磨抛光后，依次放入酒精和丙酮中超声清洗10～15min；
(2)化学镀镍：将清洗后的金属基体放入化学镀镍液中进行化学镀镍处理，其中化学镀镍液温度为80～92℃、pH值为8～10，化学镀镍处理10min结束后，将金属基体放入流动的去离子水中进行清洗处理，清洗时间15s以上，放入真空干燥箱中充分干燥后迅速放入镀膜机真空室准备下一步处理，其中镀膜机真空室本底真空度为5.0×10-3Pa～8.0×10-3Pa，加热至200～300℃，保温时间20～30min；
(3)离子清洗：向镀膜机真空室通入Ar气，其压力为0.2Pa，开启偏压电源，电压260V，占空比78，辉光放电清洗20～30min；偏压降低至190V，开启离子源离子清洗20～30min，然后开启电弧源Ti靶，偏压200～300V，靶电流65A，离子轰击Ti靶5～6min；
(4)沉积Ti：调整Ar气压至0.4～0.45Pa，偏压降低至50～60V，电弧镀Ti5～7min；
(5)沉积TiCN：调整工作气压为0.32～0.36Pa，偏压58V，Ti靶电流50～60A；开启N2，调整N2流量为50sccm，开启C2H2，调整C2H2流量为50sccm，沉积温度为120～200℃，中频磁控溅射沉积TiCN40～50min；
(6)沉积玫瑰金镀层：关闭Ti靶材，关闭N2，关闭C2H2；调整Ar气压至0.9～1.8Pa，偏压至100～200V，开启金靶电源，电流调制5～6A，中频磁控溅射沉积玫瑰金10～20min；
(7)后处理：关闭金靶电源，关闭偏压电源、离子源及气体源，保温20～25min，镀层结束；
(8)钝化处理：将镀有玫瑰金镀层的金属基体浸金银保护水，温度为30℃,钝化处理5min，取出烘干。
4.根据权利要求3所述的一种玫瑰金镀层的制备工艺，其特征在于，在化学镀镍的步骤中，其化学镀镍液的配比为：硫酸镍30～40g/L，次磷酸钠20～30g/L，氯化镍20～30g/L，苹果酸铵20～30g/L，钼酸钠5ppm。
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