Zhang Dongsheng,Wu Ning,Ren Bing,et al.Study on influencing factors on the adhesion of electroplated copper coating in HEDP system[J].Plating & Finishing,2023,(7):53-60.[doi:10.3969/j.issn.1001-3849.2023.07.007]
HEDP体系电镀铜层结合力的影响因素研究
- Title:
- Study on influencing factors on the adhesion of electroplated copper coating in HEDP system
- Keywords:
- 1-hydroxyethylidene-1 ; 1-diphosphonic acid ; electroplating copper ; coating adhesion ; surfactant
- 分类号:
- TG174.451
- 文献标志码:
- A
- 摘要:
- 羟基乙叉二膦酸（ HEDP ）镀铜是一种很有前景的无氰镀铜体系，而其中镀层结合力是保证工艺良好应用的关键之一。通过计时电位法、阴极极化曲线及划痕法等测试系统研究了 HEDP/Cu 2+ 摩尔比、表面活性剂、 pH 值、电流密度等对镀层结合力的影响规律。结果表明，上述因素均会显著影响铜层结合力。 HEDP/Cu 2+ 摩尔比小（ 2.0 ∶ 1 ）、 pH 值低（ 7~8 ）时，铁件表面存在明显置换铜，镀层结合力差；提高 HEDP/Cu 2+ 摩尔比和镀液 pH 值，铜络合物更加稳定，铜置换反应得以消除； HEDP/Cu 2+ 摩尔比超过 3.0 ∶ 1 ， pH 值大于 10 时，镀层结合良好。表面活性剂可以增强镀液对阴极界面的润湿能力，有效改善镀层结合力，且炔醇类表面活性剂表现更佳。电流密度 0.2~0.5 A/dm 2 时 Q235 钢可能处于钝态，而 2.0 A/dm 2 时镀层出现“铜瘤”，镀层结合力均不佳。
- Abstract:
- ： Electroplating copper in 1-hydroxyethylidene-1 ， 1-diphosphonic acid bath is a promising non-cyanide copper plating system ， and the coating adhesion is one of the keys to ensure the good application of this process. The influence law of HEDP/Cu 2+ molar ratio ， surfactant ， pH value and current density on the coating adhesion was systematically studied by chronopotentiometric ， cathodic polarization curve and scratch method. The results showed that the above factors can significantly affect the adhesion of copper coating. There is obvious phenomenon of copper replacement on the surface of iron parts when the molar ratio of HEDP/Cu 2+ is small （ 2.0 ∶ 1 ） and the pH value is low （ 7 - 8 ）， and the coating adhesion is poor. If increasing the HEDP/Cu 2+ molar ratio and the pH value of the bath ， the complex products of copper are more stable ， and the displacement reaction of copper is eliminated. The adhesion of copper coating is good when the HEDP/Cu 2+ molar ratio exceeds 3.0 ∶ 1 and pH > 10. Surfactant can enhance the wettability of the bath to the cathode interface and effectively improve the coating adhesion ， and the alkynol surfactant performs better. The Q235 steel may be in a passive state under 0.2 - 0.5 A/dm 2 ， and the coating will form "copper nodules" at 2.0 A/dm 2 ， and the coating adhesion is poor.
参考文献/References:
[1] 秦足足 , 李建三 , 徐金来 . 国内外无氰镀铜工艺研究进展 [J]. 电镀与涂饰 , 2015, 34(3): 149-152.
[2] 邹忠利 , 李宁 , 王殿龙 , 等 . 钢铁基体无氰碱性镀铜的研究进展 [J]. 电镀与环保 , 2008, 28(2): 9-13.
[3] 张志梁 , 张迎 . 钢铁基体无预镀直接强酸性镀铜工艺 [J]. 材料保护 , 2021, 54(7): 89-92.
[4] 杨防祖 , 蒋义锋 , 田中群 , 等 . 无氰镀铜资讯 [J]. 电镀与精饰 , 2013, 35(11): 9-14, 46.
[5] 叶成茁 , 丁运虎 , 徐九生 , 等 . 硫酸盐型滚镀厚铜研究 [J]. 材料保护 , 2021, 54(12): 111-114.
[6] 方景礼 . 钢铁件 HEDP 直接镀铜工艺开发 30 年回顾第二部分— HEDP 碱性镀铜的性能与维护要点 [J]. 电镀与涂饰 , 2009, 28(10): 1-3.
[7] 庄瑞舫 . 羟基乙叉二膦酸电解液镀铜的研究和生产应用 (Ⅰ) —镀铜工艺和电沉积机理 [J]. 电镀与精饰 , 2012, 34(8): 10-13.
[8] 庄瑞舫 . 羟基乙叉二膦酸电解液镀铜的研究和生产应用 (II) —镀液、镀层性能及镀液维护 [J]. 电镀与精饰 , 2012, 34 (9): 12-16.
[9] Gerasimenko A A, Kirvoruchko M P, Korzhavina V V. Enhancing the adhesion of copper electroplates to steel substrates cyanide-free alkaline baths[J]. Protection of Metals, 2000, 36(3): 285-288.
[10] 袁诗璞 . 钢铁件直接焦磷酸盐镀铜结合力不良的关键 [J]. 电镀与精饰 , 2009, 31(7): 18-20.
[11] 冯丽婷 , 刘清 , 冯绍彬 , 等 . 提高羟基亚乙基二膦酸直接镀铜结合强度的研究 [J]. 材料保护 , 2007, 42(9): 1-3, 82.
[12] 邱媛 , 元泉 , 杨志业 , 等 . 添加剂对 HEDP 镀铜溶液性能的影响 [J]. 电镀与精饰 , 2022, 44(5): 33-38.
[13] 秦足足 , 李建三 , 徐金来 . HEDP 溶液体系无氰镀铜配方优化 [J]. 电镀与涂饰 , 2016, 35(7): 345-350.
[14] Wada H, Fernando Q. Determination of formation constants of copper(II) complexes of ethane-1-hydroxy-1,l-diphosphonic acid with a solid state cupric ion-selective electrode [J]. Analytical Chemistry, 1971, 43(6): 751-755.
[15] Li M G, Wei G Y, Li M, et al. Effect of HEDP on copper electroplating from non-cyanide alkaline baths [J]. Surface Engineering, 2014, 30 (10): 728-734.
[16] 文庆杰 , 彭华领 , 稽海 , 等 . 表面活性剂对 HEDP 镀铜层致密度的影响 [J]. 电镀与精饰 , 2020, 42 (3): 12-17.
[17] 张鲜君 , 廖志祥 , 刘静 , 等 . 炔醇类添加剂对 HEDP 体系中铜电沉积行为的影响 [J]. 电镀与涂饰 , 2022, 41(13): 901-906.
[18] Zheng J W, Chen H B, Cai W, et al. Mechanisms of triethanolamine on copper electrodeposition from 1-hydroxyethylene-1,1-diphosphonic acid electrolyte [J]. Journal of the Electrochemical Society, 2017, 164 (12): D798-D801.
[19] 张骐 , 张安琴 , 骆晨 , 等 . 电流密度对 5,5- 二甲基乙内酰脲体系电镀银的影响 [J]. 电镀与涂饰 , 2021, 40(3): 183-186.
[20] 冯绍彬 , 商士波 , 包祥 , 等 . 电位活化现象与金属电沉积初始过程的研究 [J]. 物理化学学报 , 2005, 21(5): 463-467.
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备注/Memo
收稿日期： 2022-10-30 修回日期： 2022-11-29 作者简介： 张东升（ 1994 ―），男，硕士，工程师， email ： 1319220275@qq.com * 通信作者： 王帅星， email ： wsxxpg@126.com 基金项目： 江西省自然科学基金（ 20212BAB204043 ）?/html>