CN103540942A - 金属基体表面处理方法及其制品 - Google Patents

金属基体表面处理方法及其制品 Download PDF

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CN103540942A
CN103540942A CN201210236889.4A CN201210236889A CN103540942A CN 103540942 A CN103540942 A CN 103540942A CN 201210236889 A CN201210236889 A CN 201210236889A CN 103540942 A CN103540942 A CN 103540942A
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color layers
layer
goods
surface treatment
titanium
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CN103540942B (zh
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丁亭
曹达华
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Shenzhen Futaihong Precision Industry Co Ltd
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Shenzhen Futaihong Precision Industry Co Ltd
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Abstract

本发明提供一种金属基体表面处理方法，其包括如下步骤：提供一金属基体；采用真空镀膜的方式，在该金属基体上依次形成第一颜色层和第二颜色层，该第一颜色层为碳化钛层或氮化钛层，该第二颜色层为碳化铬层或氮化铬层，该第一颜色层与该第二颜色层呈现出不同的颜色；于该第二颜色层上形成一感光油墨层；采用曝光显影处理，使所述感光油墨层的部分区域形成一硬化层；采用电化学蚀刻处理，使第二颜色层形成至少一贯通第二颜色层的凹部，并使该第一颜色层对应所述凹部区域的表面形成氧化钛层；用以进行所述电化学蚀刻处理的处理液为含有高锰酸钾、硫酸的水溶液或氢氧化钠溶液。本发明还提供了一种经上述金属基体表面处理方法制得的制品。

Description

金属基体表面处理方法及其制品
技术领域
本发明涉及一种金属基体表面处理方法及其制品。
背景技术
现有技术，通常采用如下方法在金属基体表面制作具有双色效果的装饰性图案：先通过真空镀膜的方式，依次在金属基体表面形成一第一颜色层及第二颜色层，该第二颜色层的颜色不同于第一颜色层；采用菲林或油墨对第二颜色层部分区域进行遮蔽；采用化学蚀刻的方式，去除未被遮蔽的第二颜色层，使部分第一颜色层裸露出来。该化学蚀刻处理所采用的蚀刻液的主要成分为高锰酸钾和硫酸。由于蚀刻液浓度过大时，反应速度较快，第二颜色层及第一颜色层均被蚀刻去除；而蚀刻液浓度过小时，蚀刻液对第二颜色层及第一颜色层均没有蚀刻作用。上述两种情况均难以使金属基体表面呈现较佳的双色效果。另外，即使将蚀刻液调整为合适的浓度，在完成对第二颜色层的蚀刻至将金属基体从蚀刻液中取出的这段时间内，停留在金属基体上的蚀刻液将发生侧蚀，使第一颜色层被蚀刻，如此将降低预计形成于金属基体表面的图案的精度。
发明内容
鉴于此，本发明提供一种可解决上述问题的金属基体表面处理方法。
另外，还提供一种经上述金属基体表面处理方法制得的制品。
一种金属基体表面处理方法，其包括如下步骤：
提供一金属基体；
采用真空镀膜的方式，在该金属基体上依次形成第一颜色层和第二颜色层，该第一颜色层为碳化钛层或氮化钛层，该第二颜色层为碳化铬层或氮化铬层，该第一颜色层与该第二颜色层呈现出不同的颜色；
于该第二颜色层上形成一感光油墨层；
采用曝光显影处理，使所述感光油墨层的部分区域形成一硬化层；
采用电化学蚀刻处理，去除未被硬化层覆盖的区域的第二颜色层，使第二颜色层形成至少一贯通第二颜色层的凹部，并使该第一颜色层对应所述凹部区域的表面形成氧化钛层；用以进行所述电化学蚀刻处理的处理液为含有高锰酸钾、硫酸的水溶液或氢氧化钠溶液，当蚀刻液为含有高锰酸钾、硫酸的水溶液时，通过蚀刻液的电流密度为3~5A/dm 2，处理时间为6~9min；当蚀刻液为氢氧化钠溶液时，通过蚀刻液的电流密度为1~3A/dm 2，处理时间为1~2min；
去除所述硬化层。
一种制品，包括金属基体、依次形成于金属基体上的第一颜色层和第二颜色层，该第一颜色层为碳化钛层或氮化钛层，该第二颜色层为碳化铬层或氮化铬层，该第一颜色层与该第二颜色层呈现出不同的颜色；第二颜色层形成至少一贯通的凹部，该第一颜色层对应所述凹部区域的表面形成有氧化钛层。
本发明采用电化学蚀刻处理，通过控制电流密度和处理时间，使未被硬化层所覆盖的第二颜色层被蚀刻去除，裸露出部分第一颜色层，并可在该第一颜色层裸露的表面形成氧化钛层，避免第一颜色层被蚀刻液侵蚀，因而可使所述制品同时呈现出第一颜色层的颜色及第二颜色层的颜色。该制品的制备方法简单，精度高。
附图说明
图1为本发明较佳实施例的金属基体表面形成有第一颜色层、第二颜色层及感光油墨层的剖视示意图。
图2为图1所述金属基体表面形成有硬化层和可溶解层的示意图。
图3为图2所述金属基体去除所述可溶解层的示意图。
图4为图3所述金属基体表面形成有凹部的示意图。
图5为本发明一较佳实施例的制品的示意图。
图6是本发明一较佳实施例真空镀膜机的示意图。
主要元件符号说明
制品 100
金属基体 11
衬底层 13
第一颜色层 15
氧化钛层 151
结合层 17
第二颜色层 19
凹部 191
真空镀膜机 200
镀膜室 20
轨迹 21
钛靶 22
铬靶 23
气源通道 24
真空泵 30
感光油墨层 40
硬化层 41
可溶解层 43
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
请参阅图1，本发明较佳实施例的金属基体表面处理方法主要包括如下步骤：
提供一金属基体11，对所述金属基体11进行抛光，并将抛光后的金属基体11放入盛装有乙醇及/或丙酮溶液的超声波清洗器中进行震动清洗，以除去金属基体11表面的杂质和油污。清洗完毕后烘干备用。所述金属基体11的材质可为不锈钢、钛合金、镁合金或铝合金等。
结合参阅图6，提供一真空镀膜机200，该真空镀膜机200包括一镀膜室20、连接于镀膜室20的一真空泵30及一膜厚仪(未图示)。真空泵30用以对镀膜室20抽真空。该镀膜室20内设有转架(未图示)、相对设置的二钛靶22及二铬靶23。转架带动金属基体11沿圆形的轨迹21公转，且金属基体11在沿轨迹21公转时亦自转。每一钛靶22及每一铬靶23的两端均设有气源通道24，气体经该气源通道24进入所述镀膜室20中。
采用磁控溅射镀膜法，在该金属基体11上溅镀一衬底层13。该衬底层13为钛层。溅镀该衬底层13在所述真空镀膜机200中进行。将所述镀膜室20抽真空至6.0×10-3~8.0×10-3Pa，开启钛靶22，并设置钛靶22的功率为8~10kw；以氩气为工作气体，调节氩气的流量为150~200sccm。溅镀时，对金属基体11施加-120~-150V的偏压，并加热所述镀膜室20至温度为100~120℃（即镀膜温度为100~120℃），镀膜时间为5~8min。该衬底层13的厚度为0.1~0.2μm。
采用磁控溅射镀膜法，在所述衬底层13上溅射一第一颜色层15。该第一颜色层15为碳化钛层。保持所述镀膜温度、氩气的流量不变，设置钛靶22的功率为8~10kw；以乙炔为反应气体，向镀膜室20内通入流量为30~120sccm的乙炔；对金属基体11施加-100~-120V的偏压，镀膜时间为50~70min。该镀膜结束后，关闭所述钛靶22。所述第一颜色层15的厚度为0.8~1.1μm。
由于形成该第一颜色层15时，通入的反应气体乙炔流量较小（30~120sccm），第一颜色层15中钛元素主要以单质的形式存在。本实施例中，所述第一颜色层15呈现的色度区域于CIE LAB表色系统的L*坐标介于28至35，a*坐标介于-1至2，b*坐标介于-1至2，表现为黑色。
可以理解的，根据实际生产需要，可通过控制乙炔的流量、镀膜时间等参数，使第一颜色层15呈现出不同的颜色。
采用磁控溅射法，在所述第一颜色层15上形成一结合层17，以提高后续形成的膜层与第一颜色层15之间的结合力。该结合层17为铬层。保持所述镀膜温度、氩气的流量不变，设置钛靶22的功率为8~10kw；对金属基体11施加-100~-120V的偏压，镀膜时间为5~8min。所述结合层17的厚度为0.1~0.2μm。
采用磁控溅射镀膜法，在所述结合层17上溅射一第二颜色层19。该第二颜色层19为碳化铬层。保持所述镀膜温度、氩气的流量不变，设置铬靶23的功率为8~10kw；以乙炔为反应气体，向镀膜室20内通入流量为30~60sccm的乙炔；对金属基体11施加-100~-120V的偏压，镀膜时间为90~120min。所述第二颜色层19的厚度为1~1.2μm。
本实施例中，所述第二颜色层19呈现的色度区域于CIE LAB表色系统的L*坐标介于68至75，a*坐标介于0至3，b*坐标介于0至3，表现为银白色。
可以理解的，可通过控制乙炔的流量、镀膜时间等参数，使第二颜色层19呈现出不同的颜色。
采用喷涂或印刷的方式，于所述第二颜色层19上涂覆一感光油墨层40，所述感光油墨层40的厚度为40~60μm。
结合参见图2及图3，采用曝光处理，使所述感光油墨层40形成有硬化层41和可溶解层43；并通过显影处理，将所述可溶解层43的感光油墨溶解在显影液中，而所述硬化层41仍附着在该第二颜色层19上。
结合参见图4，对经曝光显影处理后的金属基体11进行电化学蚀刻处理，去除未被硬化层41覆盖的区域的第二颜色层19及结合层17，形成至少一凹部191。
所述电化学蚀刻处理的方法为：使用含有高锰酸钾、硫酸的水溶液作为该电化学蚀刻处理的蚀刻液，其中，高锰酸钾的质量百分含量为5~10%，硫酸的质量百分含量为10~15%。以金属基体11为阳极，以铅板为阴极，将金属基体11和铅板置于该蚀刻液中，进行电解蚀刻。所述蚀刻液的温度为20~30℃，通过蚀刻液的电流密度为3~5A/dm 2，处理时间为6~9min。
可以理解的，所述蚀刻液还可为氢氧化钠溶液，该氢氧化钠溶液的质量百分含量为5~8%。当采用氢氧化钠溶液作为蚀刻液时，氢氧化钠溶液的温度为20~30℃，通过氢氧化钠溶液的电流密度为1~3A/dm 2，处理时间为1~2min。
在该电化学蚀刻处理过程中，未被硬化层41覆盖的区域的结合层17和第二颜色层19将溶解在所述蚀刻液中。同时，作为阳极的金属基体11将发生如下反应：4OH-=O2+2H2O+4e，生成氧气。当未被硬化层41覆盖的结合层17和第二颜色层19被溶解，使所述第一颜色层15裸露出来时，所述阳极生产的氧气将与裸露的第一颜色层15中的单质钛反应在第一颜色层15表面形成一层致密的氧化钛层151。该氧化钛层151不易溶于所述蚀刻液，可阻碍所述第一颜色层15被蚀刻掉。该氧化钛层151的厚度为1~3nm。因氧化钛层151的厚度较薄，氧化钛层151的形成对该第一颜色层15的颜色几乎没有影响。
采用含有高锰酸钾、硫酸的水溶液为蚀刻液时，为了使经电化学蚀刻处理后的金属基体11表面呈现出具有双色效果的图案外观，需保证电流密度为3~5A/dm 2。当电流密度大于5A时，蚀刻速度较快，难以控制电化学蚀刻的强度，第一颜色层15易于被蚀刻液去除。当电流密度小于3A时，去除该第二颜色层19及结合层17的时间增加，提高了生产成本。另外，在控制电流密度的同时，还需保证电化学蚀刻处理的时间为6min~9min。当处理时间小于6min时，第二颜色层19与结合层17不能完全反应而褪除；当处理时间大于9min时，第一颜色层15易于被去除。控制所述电化学蚀刻处理的时间，还可避免形成的氧化钛层151过厚而影响金属基体11的外观。
同理，采用氢氧化钠溶液为蚀刻液时，也需保证电流密度为1~3A/dm 2、处理时间为1~2min，以使金属基体11呈现双色效果的图案外观。
结合参见图5，去除所述硬化层41，使被硬化层41所覆盖的部分第二颜色层19裸露出来。
本发明还提供一种经上述方法制得的制品100。该制品100包括一金属基体11、依次形成于金属基体11上的衬底层13、第一颜色层15、结合层17及第二颜色层19。该制品100上形成有至少一凹部191，该凹部191贯穿所述第二颜色层19及结合层17。该第一颜色层15与第二颜色层19呈现出不同的颜色。
该衬底层13为钛层。该衬底层13的厚度为0.1~0.3μm。
该第一颜色层15为碳化钛层。该第一颜色层15对应形成所述凹部191区域的表面形成有氧化钛层151。该氧化钛层151的厚度为1~3nm。该第一颜色层15未形成有氧化钛层151的区域的厚度为0.8~1.1μm。所述氧化钛层151呈现的色度区域于CIE LAB表色系统的L*坐标介于28至35，a*坐标介于-1至2，b*坐标介于-1至2，其与第一颜色层15的色度区域一致，表现为黑色。该氧化钛层151表面的粗糙度Ra为0.1~0.3μm。
该结合层17为铬层。该结合层17的厚度为0.1~0.2μm。
该第二颜色层19为碳化铬层。所述第二颜色层19呈现的色度区域于CIE LAB表色系统的L*坐标介于68至75，a*坐标介于0至3，b*坐标介于0至3，表现为银白色。该第二颜色层19的厚度为1~1.2μm。
所述凹部191的深度为1.1~1.4μm。所述凹部191作为一个整体可呈现出所需要的图案、文字、商标等。
可以理解的，所述第一颜色层还可为氮化钛层。
可以理解的，所述第二颜色层还可为氮化铬层。
可以理解的，所述衬底层13可以省略。
可以理解的，所述结合层17可以省略。
本发明采用电化学蚀刻处理，通过控制电流密度和处理时间，使未被硬化层41所覆盖的第二颜色层19和结合层17被蚀刻去除，裸露出部分第一颜色层15，并可在该第一颜色层15裸露的表面形成氧化钛层151，可避免第一颜色层15被蚀刻液侵蚀，因而可使所述制品100同时呈现出第一颜色层15的颜色及第二颜色层19的颜色。该制品100的制备方法简单，精度高。

Claims (19)

1.一种金属基体表面处理方法，其包括如下步骤：
提供一金属基体；
采用真空镀膜的方式，在该金属基体上依次形成第一颜色层和第二颜色层，该第一颜色层为碳化钛层或氮化钛层，该第二颜色层为碳化铬层或氮化铬层，该第一颜色层与该第二颜色层呈现出不同的颜色；
于该第二颜色层上形成一感光油墨层；
采用曝光显影处理，使所述感光油墨层的部分区域形成一硬化层；
采用电化学蚀刻处理，去除未被硬化层覆盖的区域的第二颜色层，使第二颜色层形成至少一贯通第二颜色层的凹部，并使该第一颜色层对应所述凹部区域的表面形成氧化钛层；用以进行所述电化学蚀刻处理的处理液为含有高锰酸钾、硫酸的水溶液或氢氧化钠溶液，当蚀刻液为含有高锰酸钾、硫酸的水溶液时，通过蚀刻液的电流密度为3~5A/dm 2，处理时间为6~9min；当蚀刻液为氢氧化钠溶液时，通过蚀刻液的电流密度为1~3A/dm 2，处理时间为1~2min；
去除所述硬化层。
2.如权利要求1所述的金属基体表面处理方法，其特征在于：该含有高锰酸钾、硫酸的水溶液中，高锰酸钾的质量百分含量为5~10%，硫酸的质量百分含量为10~15%。
3.如权利要求2所述的金属基体表面处理方法，其特征在于：该电化学蚀刻处理中，该蚀刻液的温度为20~30℃。
4.如权利要求1所述的金属基体表面处理方法，其特征在于：该氢氧化钠溶液的质量百分含量为5~8%。
5.如权利要求4所述的金属基体表面处理方法，其特征在于：该电化学蚀刻处理中，该氢氧化钠溶液的温度为20~30℃。
6.如权利要求1所述的金属基体表面处理方法，其特征在于：当第一颜色层为碳化钛层时，第一颜色层通过如下方式形成：以钛靶为靶材，设置钛靶的功率为8~10kw；以乙炔为反应气体，设置乙炔的流量为30~120sccm；对金属基体施加的偏压为-100~-120V，镀膜温度为100~120℃，镀膜时间为50~70min。
7.如权利要求1所述的金属基体表面处理方法，其特征在于：当第二颜色层为碳化铬层时，第二颜色层通过如下方式形成：以铬靶为靶材，设置铬靶的功率为8~10kw；以乙炔为反应气体，设置乙炔的流量为30~60sccm；对金属基体施加的偏压为-100~-120V，镀膜温度为100~120℃，镀膜时间为90~120min。
8.如权利要求1所述的金属基体表面处理方法，其特征在于：该金属基体表面处理方法还包括在形成该第一颜色层之前，在该金属基体上形成衬底层的步骤，该衬底层为钛层。
9.如权利要求1或8所述的金属基体表面处理方法，其特征在于：该金属基体表面处理方法还包括在形成该第二颜色层之前，在第一颜色层上形成结合层的步骤，该结合层为铬层。
10.一种制品，包括金属基体，其特征在于：该制品还包括依次形成于金属基体上的第一颜色层和第二颜色层，该第一颜色层为碳化钛层或氮化钛层，该第二颜色层为碳化铬层或氮化铬层，该第一颜色层与该第二颜色层呈现出不同的颜色；第二颜色层形成至少一贯通的凹部，该第一颜色层对应所述凹部区域的表面形成有氧化钛层。
11.如权利要求10所述的制品，其特征在于：该氧化钛层的厚度为1~3nm。
12.如权利要求11所述的制品，其特征在于：该氧化钛层表面的粗糙度Ra为0.1~0.3μm。
13.如权利要求10所述的制品，其特征在于：该氧化钛层呈现的色度区域于CIE LAB表色系统的L*坐标介于28至35，a*坐标介于-1至2，b*坐标介于-1至2。
14.如权利要求11所述的制品，其特征在于：该第一颜色层未形成有氧化钛层的区域的厚度为0.8~1.1μm。
15.如权利要求11所述的制品，其特征在于：该第二颜色层的厚度为1~1.2μm。
16.如权利要求15所述的制品，其特征在于：当第二颜色层为碳化铬层时，第二颜色层呈现的色度区域于CIE LAB表色系统的L*坐标介于68至75，a*坐标介于0至3，b*坐标介于0至3。
17.如权利要求10所述的制品，其特征在于：该凹部的深度为1.1~1.4μm。
18.如权利要求10所述的制品，其特征在于：该制品还包括形成于第一颜色层和第二颜色层之间的结合层，该结合层为铬层。
19.如权利要求18所述的制品，其特征在于：该凹部贯穿所述第二颜色层及结合层。
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