陈耀,任骊,余云丹,张中泉,常菲帆,卫国英.乙内酰脲碱性无氰镀铜工艺的研究[J].表面技术,2025,54(2):243-249.
CHEN Yao,REN Li,YU Yundan,ZHANG Zhongquan,CHANG Feifan,WEI Guoying.Research on Hydantoin for Alkaline Cyanide-free Copper Plating Process[J].Surface Technology,2025,54(2):243-249 |
| 乙内酰脲碱性无氰镀铜工艺的研究 |
| Research on Hydantoin for Alkaline Cyanide-free Copper Plating Process |
| 投稿时间：2024-02-20 修订日期：2024-10-12 |
| DOI：10.16490/j.cnki.issn.1001-3660.2025.02.021 |
| 中文关键词: 电沉积铜 乙内酰脲 有机添加剂 循环伏安 择优取向 电流效率 |
| 英文关键词:copper electrodeposition hydantoin organic additives cyclic voltammetry preferred orientation current efficiency |
| 基金项目:杭州市重点科研计划项目(2023SZD0052);国家自然科学基金(52171083);浙江省自然科学基金(LQ20B020011) |
| 作者 | 单位 |
| 陈耀 | 中国计量大学 材料与化学学院，杭州 310018 |
| 任骊 | 中国计量大学 材料与化学学院，杭州 310018 |
| 余云丹 | 中国计量大学 材料与化学学院，杭州 310018 |
| 张中泉 | 中国计量大学 材料与化学学院，杭州 310018 |
| 常菲帆 | 中国计量大学 材料与化学学院，杭州 310018 |
| 卫国英 | 中国计量大学 材料与化学学院，杭州 310018 |
|
| Author | Institution |
| CHEN Yao | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
| REN Li | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
| YU Yundan | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
| ZHANG Zhongquan | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
| CHANG Feifan | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
| WEI Guoying | College of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China |
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| 中文摘要: |
| 目的 目前比较成熟的电镀铜工艺大多涉及氰化物，但相关工艺存在环保等问题，因此开发新型的无氰镀铜工艺，替代传统的氰化镀铜工艺，长期以来一直是研究的热点。方法 以氯化亚铜为铜源，选用乙内酰脲作为镀液配位剂，结合其他成分，并优化乙内酰脲浓度、镀液温度以及pH值等工艺参数，在Q235低碳钢片上实现铜的电沉积。通过极化曲线和循环伏安曲线讨论镀液的极化度和成膜机理，利用扫描电子显微镜和金相显微镜观察镀层的微观形貌，并通过X射线晶体衍射仪研究乙内酰脲添加剂对镀层中铜的成核及生长所起到的作用。计算了乙内酰脲体系电沉积铜的电流效率，通过在完整镀液中加入Q235钢片静置24 h，验证是否发生置换反应。结果 研究表明，铜的电沉积符合连续成核生长模式，循环伏安曲线表明加入乙内酰脲后在−0.73 V附近出现了铜的阴极还原峰;加入乙内酰脲和三乙烯四胺的复合添加剂使沉积电位负移，增大了极化;乙内酰脲体系所得铜镀层更为平整，结晶粒更为细小，XRD测试表明乙内酰脲体系镀铜层沿(200)晶面择优生长，相关体系的电流效率可高达91%，验证了镀液体系没有发生置换反应。该配方及工艺条件为:氯化亚铜10.0 g/L，乙内酰脲34.7 g/L，无水Na2SO4 20 g/L，三乙烯四胺0.1 g/L，NaCl 10.0 g/L，pH值9~10，温度45 ℃，电流密度2.0 A/dm2。结论 相关镀液用于无氰镀铜工艺，镀层平整致密。 |
| 英文摘要: |
| At present, cyanide copper plating is still a relatively mature electroplating process. However, the toxicity of the cyanide systems may lead to high wastewater treatment cost and safety hazards. As a result, it has been a research hotspot for a long time that developing a new cyanide-free copper plating process in order to substitute the traditional cyanide copper plating processes. The existing cyanide free copper electroplating process also has some problems, such as poor adhesion and insufficient surface refinement of the coating. In addition, the stability of the plating solution is also important due to practical applications. In this work, the formulation of a cyanide-free copper plating process was obtained from cuprous chloride aqueous solution, with hydantoin and other components as the organic additives. In addition, the concentration of hydantoin, the temperature and the pH value of the solution were all optimized in order to get a better result. The effects of different current densities on the coating were explored through a hull cell test. The redox process of the system was studied via polarization curves and cyclic voltammetry curves, and the nucleation mechanism of copper plating in the system was studied through current time curves. The microstructure of copper coatings at different scales was observed by metallographic microscopy and scanning electron microscopy. The composition and preferred orientation of the copper coating were analyzed by X-ray diffraction, and the grain sizes were calculated. In addition, the effects on the additives of hydantoin were analyzed. Finally, the current efficiency of the hydantoin system was obtained by measuring multiple samples and calculating their current efficiencies by the weight under the optimized conditions. By measuring the current time curves of electrodeposited Cu at different potentials, the nucleation curve of copper was obtained and indicated that the electrodeposition of copper conformed to the continuous nucleation growth mode. The addition of the additives, which was composed of hydantoin and triethylenetetramine negatively shifted the deposition potential and increased the polarization. The copper coating obtained by the hydantoin system was smoother. The crystal grain was better. The XRD test showed that the copper coating of the hydantoin system grew preferentially along the (200) crystal plane, hydantoin promoted the nucleation and growth of Cu in the coating and the current efficiency of the related system could be as high as 91%, which verified that no displacement reaction occurred in the plating solution system. The best formulation of the alkaline cyanide-free copper plating process were:cuprous chloride of 10.0 g/L, sodium sulfate of 20 g/L, hydantoin of 34.7 g/L, triethylenetetramine of 0.1 g/L, NaCl of 10.0 g/L, pH=9-10, temperature of 45 ℃ and current density of 2.0 A/dm2. The solution is used for cyanide-free copper plating process, and the plating layer is smooth and dense. This research studies on the performance and role of hydantoin and its derivatives in copper electroplating, and develops a new alkaline cyanide free copper electroplating process, which is of great practical significance for promoting clean and safe electroplating production and reducing environmental pollution caused by electroplating. |
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