金属-聚合物直接成型技术中铜的表面处理

doi:10.16183/j.cnki.jsjtu.2019.185

摘要/Abstract

摘要：

研究铜的表面微纳米结构制备工艺并进行了优化．使用碳酸钠和钼酸钠的水溶液作为电解液，在恒定电压下对铜表面进行阳极氧化，在铜表面生成一层氧化膜．使用磷酸和磷酸二氢钠的水溶液作为腐蚀液，对铜表面进行腐蚀处理，以在铜表面获取微纳米结构，并在扫描电镜下观察其形貌．统计分析扫描电镜图片，计算得到铜表面的微纳米结构的孔隙率．结果表明：阳极氧化电压为15 V，阳极氧化时间为20 min，磷酸质量分数为20%，腐蚀时间为30 min时，铜的表面形貌较为平整，孔隙率达到25.77%.根据正交实验结果，腐蚀液种类、浓度以及腐蚀时间对孔隙率的影响较大，而阳极氧化电解液、电压以及电解时间影响不明显．使用阳极氧化和化学腐蚀相结合的方法可以在铜表面制备出均匀、孔隙率高的微纳米结构．

关键词: 铜, 表面处理, 纳米注塑, 阳极氧化, 微纳结构

Abstract:

The preparation technology of micro-nano structure on copper surface is studied and optimized. Aqueous solution containing sodium carbonate and sodium molybdate is used as electrolyte, and the copper sample is anodized at a constant voltage to form a layer of oxidation on the copper surface. Then, the copper surface is treated with aqueous solution containing phosphate and sodium dihydrogen phosphate as corrosion solution to obtain a micro-nano structure on the copper. The surface is observed by using a scanning electron microscope. Finally, the analysis software is used to analyze the scanning electron microscope image to calculate the micro-nano structure pores on the copper surface. The results show that when the anodizing voltage is 15 V, the anodizing time is 20 min, the phosphoric acid mass fraction is 20%, and the corrosion time is 30 min, the copper surface is relatively smooth, and the porosity reaches 25.77%. Orthogonal experiments demonstrate that the type, concentration of the corrosive solution, and etching time have a great effect, while the anodizing electrolyte, voltage and electrolysis have no significant effect on the porosity. Using a combination of anodic oxidation and chemical corrosion, micro and nano junctions with uniform and high porosity can be prepared on the copper surface.

Key words: copper, surface treatment, nano injection molding, anodic oxidation, micro-nano structure

中图分类号:

TQ153.6

郭荣盛, 胡广洪, 荣建, 王元龙. 金属-聚合物直接成型技术中铜的表面处理[J]. 上海交通大学学报, 2021, 55(1): 96-102.

GUO Rongsheng, HU Guanghong, RONG Jian, WANG Yuanlong. Copper Surface Treatment in Metal-Polymer Direct Molding Technology[J]. Journal of Shanghai Jiao Tong University, 2021, 55(1): 96-102.

图/表 10

图1

表1

图2

图3

表2

图4

表3

表4

图5

表5

参考文献 17

[1]	周雄，胡广洪. 基于正交实验优化不锈钢表面纳米孔结构制备工艺[J]. 表面技术，2019, 48(1): 161-167.
	ZHOU Xiong, HU Guanghong. Preparation process of nanoporous structure on stainless steel surface by orthogonal experimental methods [J]. Surface Technology, 2019, 48(1): 161-167.
[2]	李颖，梅园，王颖，等. 面向金属/树脂复合材料的纳米注塑成型技术综述[J]. 材料导报，2018, 32(13): 2295-2303.
	LI Ying, MEI Yuan, WANG Ying, et al. The state-of-art of nano-molding technique applying to the production of metal/polymer composites [J]. Material Reports, 2018, 32(13): 2295-2303.
[3]	樊聪，胡广洪，凌成智. 聚合物-金属直接成型技术[J]. 上海交通大学学报，2018, 52(2): 176-181.
	FAN Cong, HU Guanghong, LING Chengzhi. Polymer-metal direct molding technology [J]. Journal of Shanghai Jiao Tong University, 2018, 52(2): 176-181.
[4]	胡广洪，杜彦丽. 聚合物-金属组合成型及其关键技术[J]. 上海塑料，2015, 1(4): 6-10.
	HU Guanghong, DU Yanli. Polymer-to-metal hybrid technology and its key techniques [J]. Shanghai Plastics, 2015, 1(4): 6-10.
[5]	GRUJICIC M, SELLAPPAN V, OMAR M A, et al. An overview of the polymer-to-metal direct-adhesion hybrid technologies for load-bearing automotive components [J]. Journal of Materials Processing Technology, 2008, 197(1/2/3): 363-373.
[6]	比亚迪股份有限公司．一种金属-树脂复合体及其制备方法： CN201410305849.X[P].2015-12-30[2019-06-10]．
	BYD Company Limited. A metal-resin complex and a preparation method of its preparation: CN201410305849.X [P].2015-12-30[2019-06-10]．
[7]	SALGIN B, ÖZKANAT Ö, MOL J M C, et al. Role of surface oxide properties on the aluminum epoxy interfacial bonding [J]. The Journal of Physical Chemistry, 2013, 117(9): 4480-4487.
[8]	OZAWA T, KATOH K, MAEDA M. Friction stir lap welding of thermoplastic resins to 3003 aluminum alloy [J]. Journal of Japan Institute of Light Metals, 2015, 65(9): 403-405.
[9]	东莞劲胜精密组件股份有限公司．一种塑料与金属复合材料及其制造方法： CN 201310231734.6[P]. 2013-10-09[2019-06-10]．
	JANUS (Dongguan) Precision Components Co., Ltd. A metal-resin complex and a manufacturing method of its preparation: CN 201310231734.6[P]. 2013-10-09[2019-06-10]．
[10]	MERTENS A J, SENTHILVELAN S. Effect of mating metal gear surface texture on the polymer gear surface temperature [J]. Materials Today Proceedings, 2015, 2(5): 1763-1769.
[11]	KIM J Y, AHN K, JEONG S Y, et al. Enhancement of adhesion between polyphenylene sulfide and copper by surface treatments [J]. Current Applied Physics, 2014, 14(1): 118-121.
[12]	FEISTAUER E, GUIMAR E M, EBEL T, et al. Ultrasonic joining: A novel direct-assembly technique for metal-composite hybrid structures [J]. Materials Letters, 2016, 170(22): 1-4.
[13]	KIM W S, KIM K H, JANG C J, et al. Micro-and nano-morphological modification of aluminum surface for adhesive bonding to polymeric composites [J]. Journal of Adhesion Science and Technology, 2013, 27(15): 1625-1640.
[14]	YEH R Y, HSU R Q. Development of ultrasonic direct joining of thermoplastic to laser structured metal [J]. International Journal of Adhesion and Adhesives, 2015, 65(1): 28-32.
[15]	OCHOA-PUTMAN C, VAIDYA U K. Mechanisms of interfacial adhesion in metal-polymer composites—Effect of chemical treatment [J]. Composites Part A: Applied Science and Manufacturing, 2011, 42(8): 906-915.
[16]	KIM W S, KIM K H, JANG C J, et al. Micro-and nano-morphological modification of aluminum surface for adhesive bonding to polymeric composites[J]. Journal of Adhesion Science and Technology, 2013, 27(15): 1625-1640.
[17]	LIU F C, LIAO J, NAKATA K. Joining of metal to plastic using friction lap welding [J]. Materials and Design, 2014, 54(1): 236-238.

水平	w(H₃PO₄)/%	w(NaH₂PO₄)/%	t₁/s	t₂/s	w(Na₂CO₃)/%	U/V
1	16	1	1 320	720	5	12
2	17	2	1 440	840	10	14
3	18	3	1 560	960	15	16
4	19	4	1 680	1 080	20	18
5	20	5	1 800	1 200	25	20

元素	质量分数%
Cu	97.88
O	1.24
C	0.88

i	K(i，f)
i	f=w(H₃PO₄)	f=w(NaH₂PO₄)	f=t₁	f=t₂	f=w(Na₂CO₃)	f=U
1	0.092 9	0.140 7	0.172 1	0.171 2	0.168 1	0.168 0
2	0.149 2	0.179 1	0.171 4	0.170 7	0.174 3	0.160 6
3	0.202 1	0.166 0	0.174 8	0.145 6	0.176 0	0.161 7
4	0.197 1	0.177 2	0.188 9	0.188 6	0.156 3	0.203 9
5	0.215 8	0.194 2	0.156 0	0.187 1	0.188 6	0.168 9
R	0.122 9	0.053 5	0.032 9	0.043 0	0.032 3	0.043 3

实验组	孔径/nm	实验组	孔径/nm
1	800	4	1 300
2	1 300	5	1 500
3	1 100	平均值	1 200