| CHEN Yao,REN Li,YU Yundan,ZHANG Zhongquan,CHANG Feifan,WEI Guoying.Research on Hydantoin for Alkaline Cyanide-free Copper Plating Process[J],54(2):243-249 |
| Research on Hydantoin for Alkaline Cyanide-free Copper Plating Process |
| Received:February 20, 2024 Revised:October 12, 2024 |
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| DOI：10.16490/j.cnki.issn.1001-3660.2025.02.021 |
| KeyWord:copper electrodeposition hydantoin organic additives cyclic voltammetry preferred orientation current efficiency |
| Author | Institution |
| CHEN Yao |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
| REN Li |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
| YU Yundan |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
| ZHANG Zhongquan |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
| CHANG Feifan |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
| WEI Guoying |
College of Materials and Chemistry, China Jiliang University, Hangzhou , China |
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| Abstract: |
| 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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