CN108546910A - 一种轮毂耐老化镀膜及形成该保护膜的方法 - Google Patents

一种轮毂耐老化镀膜及形成该保护膜的方法 Download PDF

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CN108546910A
CN108546910A CN201810213141.XA CN201810213141A CN108546910A CN 108546910 A CN108546910 A CN 108546910A CN 201810213141 A CN201810213141 A CN 201810213141A CN 108546910 A CN108546910 A CN 108546910A
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plated film
coating
film
powder
wheel hub
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王再德
马焕明
李军甫
张胜超
陈广才
刘猛
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CITIC Dicastal Co Ltd
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Priority to EP19161940.2A priority patent/EP3539679A1/en
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Abstract

本发明公开了一种轮毂耐老化镀膜，依次包括：铝合金基体、硅烷转化膜、高光有机树脂涂层、周期变量合金黑铬镀膜、透明树脂涂层。本镀膜增加黑铬镀膜厚度，根据C不同含量，调整黑格的黑度。改善沉积金属层的应力残留，解决镀膜加热、快速冷却时龟裂问题；提高镀膜与底层高光树脂材料结合力问题。本发明还公开了一种轮毂耐老化镀膜的形成方法，所述的方法为：（1）硅烷预处理、（2）高光介质粉、（3）PVD镀膜、（4）喷涂透明粉。

Description

一种轮毂耐老化镀膜及形成该保护膜的方法
技术领域
本发明涉及一种表面处理领域，具体地涉及一种轮毂耐老化镀膜及形成该保护膜的方法。
背景技术
气相淀积表面处理方式有蒸镀、等离子多弧溅镀、磁控溅射及反应溅镀。磁控溅镀广泛应用在汽车零部件制造业，汽车轮毂应用磁控溅镀作为表面装饰在售后市场得到应用和推广，其特点是为了使零部件表面达到金属镜面光泽装饰效果，与传统涂装相结合，不仅美观大方，而且涂层性能可以达到汽车厂标准。
磁控溅射是在真空室，把工作气体电离，电离后的离子在电场和磁场混合场作用下高速撞击到金属靶上，使靶材上的金属原子或离子飞溅出来，沉积到工件表面上的方法。此方法可以得到光亮镜面的金属外观新效果，绿色环保、成本低。靶材可以是非磁性金属、非金属或合金，根据主机厂涂层耐腐蚀标准，选择适当的金属或合金，达到表面耐腐蚀性、耐候性、装饰性等要求。铝合金铸造轮毂表面比较粗糙，直接进行镀膜，不能形成平整光亮的镀膜，因此必须在轮毂上喷上有机涂层，再在光亮的有机涂层上进行溅镀金属膜，为了延长金属镀膜长久的光泽感，再在镀膜上进行喷涂透明粉涂层，因此镀膜材料与上下有机涂层达到良好的结合力，镀膜本身也要有高耐腐蚀性能。
采用磁控溅镀的方法三类：一类方式是白亮的金属镀膜上面喷漆黑色透明漆，达到黑亮的黑铬外观；一类方式是高光树脂为黑色，降低镀膜厚度，使得镀膜达到半透明状态，透射出底层黑色，达到黑亮；以上这两种形式各有优缺点，第一种方式带颜色的透明漆容易产生色差，黑色透明漆厚度不同，颜色不同，而且黑色透明涂层的喷涂厚度一般只有10-30微米，对镀膜的保护较差，不能达到长久使用标准；第二种方式半透镀膜不能完全遮盖底层树脂，长期暴晒，紫外老化产生层间附着力不合格。
发明内容
因此，本发明的目的是提供既可以产生黑亮金属颜色、又可以达到一定的厚度遮盖底层树脂、耐老化性能优越的合金黑铬镀膜及形成该保护膜的方法。
一种轮毂耐老化镀膜，所述镀膜的依次包括：铝合金基体、硅烷转化膜、高光有机树脂涂层、周期变量合金黑铬镀膜、透明树脂涂层。
所述的硅烷转化膜，采用硅烷前处理钝化处理工艺，主要提高铝合金与有机涂层结合力和铝合金表面耐腐蚀性能。所述的高光有机树脂涂膜是环氧树脂涂层，环氧树脂粉末涂料采用静电喷涂在铝合金轮毂表面，经过烘箱固化形成光洁度极高的涂层。所述的周期变量合金黑铬镀膜是用高纯C靶和高纯Cr靶，设置不同的镀膜工艺得到C-Cr周期变量合金黑铬镀膜。C成分90%-0周期变化，Cr金属成分10%-100%周期变化，两种材料按照以上合金成分，周期性变化，达到黑金属色，调整C靶的功率，形成的镀膜成分不同，得到黑度不同的黑铬合金镀膜；
以及所述的透明树脂膜是纯丙烯酸树脂涂层，采用静电粉末喷涂，在镀膜上形成高透明涂层。
所述的周期变量合金黑铬镀膜由C、Cr两种材料组成，其中每种材料元素所含百分比不同，镀膜颜色的不同。
所述的高光有机树脂涂层的厚度是120～250μm，充分遮盖铝合金铸造面和机加工刀纹，使铝合金轮毂表面光洁平整的镜面效果。
所述的C-Cr轮毂耐老化周期变量合金黑铬镀膜，镀膜先进行Cr打底，厚度5-10nm，提高镀膜与有机涂层的结合力，然后开启双靶，C和Cr按照比例10:90到90:10周期变化镀层，镀膜厚度为80-150nm，最后只开启纯Cr靶材，形成厚度5-10nm，整个膜厚度为100-170nm。
所述的透明树脂涂层的厚度是80-150μm，采用静电粉末涂层喷涂方法，充分保护镀膜，并与镀膜形成良好的结合力。
本发明还公开了一种轮毂耐老化镀膜的形成方法，所述的方法为：（1）硅烷预处理、（2）高光介质粉、（3）PVD镀膜、（4）喷涂透明粉。
硅烷预处理，所述的预处理步骤包括热水洗+脱脂碱洗+热水洗+水洗+酸洗+纯水洗+纯水洗+硅烷钝化+纯水洗+封闭+纯水洗+水分烘干。
喷涂高光粉末涂层，是指在轮毂金属表面采用静电喷涂环氧粉末涂料，进行固化，所述的底粉是环氧树脂粉末，也可以采用聚酯粉末涂料。涂层固化后表面达到镜面光洁度，与铝基体有良好的附着力。
PVD镀膜，是指固化完介质粉后的轮毂表面上进行高真空磁控溅镀，所述的溅镀靶材包括纯Ｃ靶材和纯Cr金属靶材，两个靶材根据颜色设定不同的功率，按照工艺先后开启镀膜，轮毂在设备里可以进行自传、公转，达到Ｃ，Cr一定先后和比例的溅镀到轮毂表面，轮毂的公转和自传使表面镀膜厚度均一，颜色一致，镀膜与底层高光树脂涂层具有了想好的结合力。
喷涂透明粉，是指PVD镀完膜后的轮毂的表面上喷透明粉并且进行固化，所述的透明粉是丙烯酸树脂或者聚酯粉末涂料，透明涂层与镀膜具有良好结合力，树脂本身也具备耐老化及其他性能。
在本发明优选的方面，在步骤（1）对表面进行预处理的步骤，所述的预处理的步骤包括水洗+碱洗+水洗+酸洗+纯水洗+钝化+纯水洗+纯水洗+封闭+纯水洗+纯水洗+烘干，钝化为硅烷转化膜，具有优良的金属耐腐蚀性，同时绿色环保，没有重金属污染。
在本发明优选的方面，在步骤（2）中，高光介质粉，厚度是80～150μm，轮辐表面固化温度是220摄氏度，固化时间是20min，优选环氧树脂，树脂硬度2-3H最佳。底粉的颜色可以是黑色，也可以灰色。与铝合金表面具有良好的结合力，同时具有较强的耐腐蚀性能。表面达到镜面的光洁度，T-G点在80-120℃。
在步骤（3）中，镀膜工件温度为80～150℃，工作气体氩气流量为40～80cc/min，C靶和铬靶镀膜电流为15～30A，550 v≥电压≤800v；真空度为2～8*10-3Pa，双靶材镀膜时间为15～40s，所述的工作气体为99.999%氩气，镀膜环境湿度为≤50%。镀膜开启顺序，先开启纯铬3-7秒，然后双靶同时开14-24秒，最后单独镀纯铬3-7秒，C和Cr含量周期变化，生成周期变量合金黑铬镀膜。
在本发明优选的方面，在步骤（4）中，喷涂纯丙烯酸透明粉厚度是80～150μm，轮毂表面固化温度是175摄氏度，固化时间是20min，轮毂A、B、C面的厚度不能小于80μm，有效提高涂层性能。也可以喷涂聚酯透明粉固化后在喷涂丙烯酸透明漆。
本发明优点在于：增加黑铬镀膜厚度，根据C不同含量，调整黑格的黑度。改善沉积金属层的应力残留，解决镀膜加热、快速冷却时龟裂问题；提高镀膜与底层高光树脂材料结合力问题；提高镀膜和表面透明涂层结合力和结合力耐久性问题；形成黑铬光亮的颜色外观，起到美观装饰作用；涂层系统具备良好的耐腐蚀性能；镀膜厚度遮盖力强，有效阻止紫外线透过，提高耐久老化性。本发明的技术方案还可以应用于其他用途，比如笔记本外壳、汽车内饰件、卫浴管件等。
具体实施方式
除非另外地说明，本发明的实施例采用两种靶材，一种是C靶材中，C的质量百分比为99.95%，另一种是纯Cr，Cr金属纯度为99.99%。PVD设备为高真空磁控溅射镀膜机。溅镀基材采用：铝合金表面为A356.2；高光介质粉末涂料：纯环氧树脂涂料；透明涂层：纯丙烯酸透明粉末涂料。涂层检查标准：按照美国通用汽车轮毂涂装性能标准进行检查，检查项目有百格附着力、CASS、FLIFORM、耐高湿度试验、耐砾石冲击、耐热冲击试验、耐老化等。
一种轮毂耐老化镀膜的形成方法，所述的方法为：（1）硅烷预处理、（2）高光介质粉、（3）PVD镀膜、（4）喷涂透明粉。
硅烷预处理步骤包括：热水洗+脱脂碱洗+热水洗+水洗+酸洗+纯水洗+纯水洗+硅烷钝化+纯水洗+封闭+纯水洗+水分烘干；
喷涂高光粉末涂层，是指在轮毂金属表面采用静电喷涂环氧粉末涂料，进行固化，所述的底粉是环氧树脂粉末，也可以采用聚酯粉末涂料。涂层固化后表面达到镜面光洁度，与铝基体有良好的附着力。
固化完介质粉后的轮毂表面上进行高真空磁控溅镀，所述的溅镀靶材包括纯Ｃ靶材和纯Cr金属靶材，两个靶材根据颜色设定不同的功率，按照工艺先后开启镀膜，轮毂在设备里可以进行自传、公转，达到Ｃ，Cr一定先后和比例的溅镀到轮毂表面，轮毂的公转和自传使表面镀膜厚度均一，颜色一致，镀膜与底层高光树脂涂层具有了想好的结合力；镀膜工件温度为100摄氏度，工作气体流量为80cc/min，镀膜电流为C靶材15 A ，纯铬靶材30A，电压675v；真空度为5*10-3Pa，第一阶段开启纯Cr，镀膜时间6秒钟，自传公转3秒/转；第二阶段开启纯Cr和纯C双靶，镀膜时间为30s，自传公转3秒/转；第三阶段开启纯Cr，镀膜时间6秒钟，自传公转3秒/转；工作气体为99.999%氩气，镀膜环境湿度为38%。
工艺流程中的喷涂透明粉是指，PVD镀完膜后的轮毂的表面上喷透明粉并且进行固化，所述的透明粉是丙烯酸树脂或者聚酯粉末涂料，透明涂层与镀膜具有良好结合力，树脂本身也具备耐老化及其他性能。
对比例1：使用本领域一般采用的方法来制备PVD保护层。采用靶材为纯Cr单靶，黑色底粉，PVD半透膜达到黑格颜色镀膜。采用的工艺方法和涂层结构与本发明的制备方法相同。
对比例2：使用本领域一般采用的方法来制备PVD保护层。采用靶材为NiCr合金单靶，黑色底粉，PVD半透膜达到黑格颜色镀膜。采用的工艺方法和涂层结构与本发明的制备方法相同。
采用实施例1与比例1、2金属表面延展性多层溅镀涂层进行了以下的检测和对比，见下表：
组 实施例1 对比例1 对比例2
镀膜颜色 L=65.0,a=0.1,b=-2.2 L=64.5,a=0.1,b=-2.2 L=65.2,a=0.1,b=-2.2
表面龟裂 无裂痕 有裂痕 无裂痕
镀膜厚度 120nm 56nm 58nm
百格附着力 100%无脱落 100%无脱落 100%无脱落
CASS 1.0㎜ 1.1㎜ 4.2㎜
FLIFORM 2.3㎜ 3.1㎜ 5.8㎜
耐水试验 无变化，附着力100%无脱落 无变化，附着力91%无脱落 无变化，附着力77%无脱落
耐热冲击 无脱落 10%脱落 13%脱落
耐老化 无变化，附着力100%镀膜无脱落 无变化，附着力65%镀膜无脱落 无变化，附着力61%镀膜无脱落
由此可见，本发明的方法中，镀膜温度、氩气流量、镀膜电流、真空度、NiCr合金靶材和纯Cr镀膜时间为关键参数，C、Cr比例及镀膜参数是得到镀膜厚度及耐老化关键。通过优化以上的工艺，得到了性能良好的PVD镀膜。本发明中，实施例的技术方案通过摸索以上的条件得到了最佳的条件。在该最佳的条件下涂层检测实验结果最好。

Claims (3)

1.一种轮毂耐老化镀膜，其特征在于：所述镀膜的依次包括：铝合金基体、硅烷转化膜、高光有机树脂涂层、周期变量合金黑铬镀膜、透明树脂涂层。
所述的周期变量合金黑铬镀膜是C-Cr周期变量合金黑铬镀膜，C成分90%-0周期变化，Cr金属成分10%-100%周期变化，镀膜先进行Cr打底，厚度5-10nm，然后开启双靶，C和Cr按照比例10:90到90:10周期变化镀层，镀膜厚度为80-150nm，最后只开启纯Cr靶材，形成厚度5-10nm，整个膜厚度为100-170 nm；
所述的高光有机树脂涂层的厚度是120～250μm，所述的透明树脂涂层的厚度是80-150μm。
2.一种轮毂耐老化镀膜的形成方法，其特征在于：所述的方法为：（1）硅烷预处理、（2）高光介质粉、（3）PVD镀膜、（4）喷涂透明粉；
硅烷预处理，所述的预处理步骤包括热水洗+脱脂碱洗+热水洗+水洗+酸洗+纯水洗+纯水洗+硅烷钝化+纯水洗+封闭+纯水洗+水分烘干；
喷涂高光粉末涂层，是指在轮毂金属表面采用静电喷涂环氧粉末涂料，进行固化，所述的底粉是环氧树脂粉末，也可以采用聚酯粉末涂料；
PVD镀膜，是指固化完介质粉后的轮毂表面上进行高真空磁控溅镀，所述的溅镀靶材包括纯Ｃ靶材和纯Cr金属靶材，两个靶材根据颜色设定不同的功率，按照工艺先后开启镀膜，轮毂在设备里可以进行自传、公转，达到Ｃ，Cr一定先后和比例的溅镀到轮毂表面，轮毂的公转和自传使表面镀膜厚度均一，颜色一致，镀膜与底层高光树脂涂层具有了想好的结合力；
喷涂透明粉，是指PVD镀完膜后的轮毂的表面上喷透明粉并且进行固化，所述的透明粉是丙烯酸树脂或者聚酯粉末涂料，透明涂层与镀膜具有良好结合力，树脂本身也具备耐老化及其他性能。
3.根据权利要求2所述的一种轮毂耐老化镀膜的形成方法，其特征在于：在步骤（1）对表面进行预处理的步骤，所述的预处理的步骤包括水洗+碱洗+水洗+酸洗+纯水洗+钝化+纯水洗+纯水洗+封闭+纯水洗+纯水洗+烘干，钝化为硅烷转化膜；
在步骤（2）中，高光介质粉，厚度是80～150μm，轮辐表面固化温度是220摄氏度，固化时间是20min，优选环氧树脂，树脂硬度2-3H最佳；底粉的颜色可以是黑色，也可以灰色；T-G点在80-120℃。
在步骤（3）中，镀膜工件温度为80～150℃，工作气体氩气流量为40～80cc/min，C靶和铬靶镀膜电流为15～30A，550 v≥电压≤800v；真空度为2～8*10-3Pa，双靶材镀膜时间为15～40s，所述的工作气体为99.999%氩气，镀膜环境湿度为≤50%。镀膜开启顺序，先开启纯铬3-7秒，然后双靶同时开14-24秒，最后单独镀纯铬3-7秒，C和Cr含量周期变化，生成周期变量合金黑铬镀膜；
在步骤（4）中，喷涂纯丙烯酸透明粉厚度是80～150μm，轮毂表面固化温度是175摄氏度，固化时间是20min，轮毂A、B、C面的厚度不能小于80μm。
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CN106694344A (zh) * 2016-11-28 2017-05-24 中信戴卡股份有限公司 一种金属保护层及形成该金属保护层的方法

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US11072853B2 (en) 2018-03-21 2021-07-27 Citic Dicastal Co., Ltd High-ductility periodic variable alloy protective film and forming method thereof
CN110106472A (zh) * 2019-05-05 2019-08-09 中信戴卡股份有限公司 一种金属表面保护层及其制备方法
CN113774326A (zh) * 2021-08-26 2021-12-10 浙江交工新材料有限公司 一种金属波纹管表面处理方法
CN113774326B (zh) * 2021-08-26 2024-02-27 浙江交工新材料有限公司 一种金属波纹管表面处理方法

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