Reline低温熔盐体系中Gd-Mg-Co合金膜的制备及表征
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摘要
为了得到附着力好、耐腐蚀性强的稀土镁合金,在353 K油浴条件下,采用循环伏安法分别研究了Gd(Ⅲ)、Mg(Ⅱ)、Co(Ⅱ)在氯化胆碱-尿素低温熔盐体系中的电化学行为。结果表明:Co(Ⅱ)→Co为一步不可逆反应,其在Pt电极的传递系数为0.41,扩散系数为1.32×10~(-6)cm~2/s,Mg(Ⅱ)、Gd(Ⅲ)在此体系中不能单独还原为单质,可被Co(Ⅱ)诱导共沉积。由恒电位法电沉积得到的Gd-Mg-Co合金中Gd的含量随沉积电位、沉积时间、Gd~(3+)/Mg~)(2+)/Co~(2+)浓度比的改变而改变,在-1.15 V电位下,Gd~(3+)/Mg~)(2+)/Co~(2+)摩尔比为4∶3∶4、沉积20 min时,得到表面均匀的黑色合金膜。在此沉积条件下得到的合金膜经扫描电镜(SEM)、X射线衍射仪(XRD)、能谱仪(EDX)等手段进行形貌、成分分析可知,此合金膜为非晶态,在碱性溶液中具有较好的耐腐蚀性能,合金膜中Gd的质量分数高达62.41%。
In order to get rare earth magnesium alloy with good adhesion and corrosion resistance,cyclic voltammetry was used to study the electrochemical behaviors of Gd(Ⅲ),Mg(Ⅱ),Co(Ⅱ) in chlorcholine-urea low-temperature molten salt systems under 353 K oil bath condition.Results showed that the reaction of Co(Ⅱ) transforming into Co was irreversible,which had transfer coefficient of 0.41 on the Pt electrode and diffusion coefficient of 1.32×10~(-6) cm~2/s.Mg(Ⅱ) and Gd(Ⅲ) could not be reduced and deposited separately,while were always induced co-deposition by Co(Ⅱ).In addition,the Gd content in Gd-Mg-Co alloy deposited by potentiostatic method changed as the deposition potential,deposition time,and the concentration ratio of Gd~(3+)/Mg~)(2+)/Co~(2+).When the molar ratio of Gd~(3+)/Mg~)(2+)/Co~(2+) was 4 ∶ 3 ∶ 4 and deposition time was 20 min,the dense black alloy film with uniform surface was obtained at the potential of-1.15 V.By using scanning electron microscope(SEM),X-ray diffractometer(XRD) and energy dispersive spectrometer(EDX) to analyze the morphology and composition,the obtained alloy film with amorphous phase had good corrosion performance in alkaline solution,and the mass content of Gd in the alloy film reached up to 62.41%.
In order to get rare earth magnesium alloy with good adhesion and corrosion resistance,cyclic voltammetry was used to study the electrochemical behaviors of Gd(Ⅲ),Mg(Ⅱ),Co(Ⅱ) in chlorcholine-urea low-temperature molten salt systems under 353 K oil bath condition.Results showed that the reaction of Co(Ⅱ) transforming into Co was irreversible,which had transfer coefficient of 0.41 on the Pt electrode and diffusion coefficient of 1.32×10~(-6) cm~2/s.Mg(Ⅱ) and Gd(Ⅲ) could not be reduced and deposited separately,while were always induced co-deposition by Co(Ⅱ).In addition,the Gd content in Gd-Mg-Co alloy deposited by potentiostatic method changed as the deposition potential,deposition time,and the concentration ratio of Gd~(3+)/Mg~)(2+)/Co~(2+).When the molar ratio of Gd~(3+)/Mg~)(2+)/Co~(2+) was 4 ∶ 3 ∶ 4 and deposition time was 20 min,the dense black alloy film with uniform surface was obtained at the potential of-1.15 V.By using scanning electron microscope(SEM),X-ray diffractometer(XRD) and energy dispersive spectrometer(EDX) to analyze the morphology and composition,the obtained alloy film with amorphous phase had good corrosion performance in alkaline solution,and the mass content of Gd in the alloy film reached up to 62.41%.
引文
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[2]LIU P,YANG Q Q,TONG Y X,et al.Electrodeposition of rare earth metals and organic electrolytes[J].Journal of Rare Earths,1999,17(2):152-154.
[3]王小娟,李慧,王娇,等.钴锌合金在氯化胆碱-尿素离子液体中的电沉积行为[J].材料保护,2010,43(3):30-33.
[4]HUANG P C,HOU K H,WANG G L,et al.Corrosion Resistance of the Ni-Mo Alloy Coatings Related to Coating’s Electroplating Parameters[J].Int J Electrochem Sci,2015,49(10):72-84.
[5]ALI M R,RAHMAN M Z,SAHA S S.Electroless and electrolytic deposition of nickel from deep eutectic solvents based on choline chloride[J].Indian Journal of Chemical Technology,2014,21(1):127-133.
[6]杨绮琴,方北龙,童叶翔.应用电化学[M].广州:中山大学出版社,2001:1.
[7]YANG M H,SUN I W.Eletrodeposition of antimong in a water-stable 1-ethyl-3-methylimidazolium chloride tet.rafluoroborate room temperature ionic liquid[J].Journal of Applied Electrochemistry,2003,33(10):1 077-1 084.
[8]陆军.有机溶剂中稀土[Sm(Ⅲ)、Tm(Ⅲ)、Ce(Ⅲ)]离子电化学性质及合金膜制备的研究[D].西宁:青海师范大学,2015:11-33.
[9]贾梦秋,杨胜文.应用电化学[M].北京:高等教育出版社,2007:7.
[10]陈必清,王建朝,郭承育,等.乙酰胺-尿素-Na Br熔体中Gd-Ni合金的电化学制备[J].电化学,2006(2):227-231.
[11]刘影,赵美峰,田凤,等.室温乙醇中化学镀Tb-FeNi-B合金及磁性研究[J].稀土,2014(1):6-10.
[12]刘青,王建朝,张新田,等.乙酰胺-尿素-Na Br熔体中电沉积Tb-Mg-Ni合金的研究[J].山东大学学报(工学版),2006,111(6):115-120.
[13]李正元,于锦,王丽丽.低温熔盐中电沉积制备La-MgNi三元合金膜及其性能研究[J].稀有金属材料与工程,2012,20(11):2 029-2 032.
[14]张若桦.稀土元素化学[M].天津:天津科学技术出版社,2005:20-23.
[15]刘永强.小角度XRD的实现及应用[D].杭州:杭州电子科技大学,2014:34-55.