添加剂对ChCl-GlA低共熔溶剂中电沉积铜的影响  

Effect of Additives on Electrodeposition of Copper in Ch Cl-Gl A Low Eutectic Solvent

作　　者：刘洋[1] 郝建军[1] 尹鸿鹍 王薪惠 LIU Yang;HAO Jianjun;YIN Hongkun;WANG Xinhui(School of Environmental and Chemical Engineering,Shenyang Ligong University,Shenyang 110159,China;Norinco Group Aviation Ammunition Institute,Harbin 150036,China;Liaoshen Industries Group Co.,Ltd.,Shenyang 110045,China)

机构地区：[1]沈阳理工大学环境与化学工程学院,辽宁沈阳110159 [2]中国兵器工业集团航空弹药研究院有限公司,黑龙江哈尔滨150036 [3]辽沈工业集团有限公司,辽宁沈阳110045

出　　处：《材料保护》2024年第12期8-16,共9页Materials Protection

摘　　要：使用添加剂有助于铜在金属基体上的沉积,以氯化胆碱-冰醋酸(Ch Cl-Gl A)为低共熔溶剂,醋酸铜为主盐,探究抗坏血酸(C6H8O6)、乙二胺四乙酸二钠(EDTA-2Na)、二乙基三胺五乙酸(DTPA)作为添加剂对铁基体表面电沉积铜的影响。采用循环伏安法(CV)和计时电流法(CA)研究电化学行为;采用扫描电镜(SEM)和X射线衍射仪(XRD)观察分析镀层形貌和成分;采用紫外-可见-近红外分光光度计分析不同添加剂下电沉积液中形成配合物的紫外-可见吸收光谱。结果表明:在Ch Cl-Gl A中,铜的电沉积为两步氧化还原,第1步为Cu^(2+)→Cu^(+);第2步为Cu^(+)→Cu;3种添加剂均可促进Ch Cl-Gl A中铜的沉积,抗坏血酸的效果最佳,可得到性能良好的铜镀层;铜在Ch Cl-Gl A中的电沉积遵循三维瞬时成核方式且为受扩散控制的不可逆反应,Cu^(2+)和Cu^(+)的扩散系数分别为4.0039×10^(-7) cm^(2)/s,4.7627×10^(-7) cm^(2)/s;以抗坏血酸为添加剂制备的铜结晶晶形为晶粒分明的多边形片状结构,最优结晶面为(111)晶面。添加DTPA、EDTA-2Na、C_(6)H_(8)O_(6)的铜镀层的平均晶粒尺寸分别为50.71、55.12、52.73 nm,未添加添加剂的铜镀层的平均晶粒尺寸为44.73 nm。The use of additives facilitates the deposition of copper on metal substrates.In this work,using choline chloride glacial acetic acid(Ch ClGl A)as a low eutectic solvent and copper acetate as the main salt,the effects of ascorbic acid(C6H8O6),disodium ethylenediamine tetraacetic acid(EDTA2Na)and diethylenetriaminepentaacetic acid(DTPA)as additives on electrodeposition of copper on iron substrate were investigated.Electrochemical behavior was studied by cyclic voltammetry(CV)and chronoamperometry(CA);scanning electron microscopy(SEM)and Xray diffraction(XRD)were used to observe and analyze the morphology and composition of the coating.The UVvisible absorption spectrum of the complex formed in the electrodeposited solution with different additives was analyzed by a UVVisNIR spectrophotometer.Results indicated that in Ch ClGl A,the electrodeposition of copper involved two steps of oxidationreduction with the first step of Cu^(2+)→Cu^(+)and the second step of Cu^(+)→Cu.All three additives promoted the deposition of copper in Ch ClGl A,and ascorbic acid had the best effect,which could obtain a copper coating with good performance at room temperature.The electrodeposition of copper in Ch ClGl A followed a threedimensional instantaneous nucleation process and was an irreversible reaction controlled by diffusion.Moreover,the diffusion coefficients of Cu^(2+)and Cu^(+)could reach 4.0039×10^(-7) cm^(2)/s,4.7627×10^(-7) cm^(2)/s,respectively.The copper crystal prepared with ascorbic acid as additive was a polygonal sheetlike structure with distinct grains,and the optimal crystal plane was the(111)crystal plane.Besides,the average grain sizes of the copper layer with additives DTPA,EDTA2Na and C_(6)H_(8)O_(6) were 50.71,55.12 and 52.73 nm.The average grain size of the copper layer without additive was 44.73 nm.

关 键 词：电沉积铜 低共熔溶剂 添加剂 循环伏安测试 

分 类 号：TG174.45[金属学及工艺—金属表面处理]