·806· 工程科学学报，第40卷，第7期 -1.44 量分数0.3%和0.9%时，增加稍大(0.9472V和 0.9372V),纯铝为0.9077V.在500Am-2极化电 流密度下的析出电位几乎不受M元素添加的 50 影响. -1.53 1—纯A 参考文献 2-A1-0.3%Mn 3-ZAl-0.6%Mn4-Al-0.9%Mn -1.56 5一A1-1.2%Mn6-A1-1.5%Mn [1]Tafiski T,Pakiela W,Janicki D,et al.Properties of the alumin- 7-Al-2.0%Mn ium alloy EN AC-51100 after laser surface treatment.Arch Metall -1.59 Mater,.2016,61(1):199 -1.62 [2]Saleema N,Gallant D.Atmospheric pressure plasma oxidation of 0 300600900120015001800 AA6061-T6 aluminum alloy surface for strong and durable adhe- 时间 sive bonding applications.Appl Surf Sci,2013,282:98 图7不同质量分数M的铝合金电极的恒电流极化曲线 [3]Lee H J,Yang I H,Kim S K,et al.In vivo comparison between Fig.7 Galvanostatic polarization of Al alloy electrodes with different the effects of chemically modified hydrophilic and anodically oxi- Mn concentrations dized titanium surfaces on initial bone healing.Periodontal Im- plant Sci,2015,45(3):94 要是电极在极化电流作用下，达到析出电位后不断 [4]Tan Q,Li Q H,Liu Z H,et al.Current situation on removal of 有金属离子的还原与晶核的生成，改变了电极表面 fluorine and chlorine in zine hydrometallurgy.Hydrometall China, 各点的平衡电势，但随着时间的延长，电极电压整体 2015,34(4):264 趋于稳定平衡状态20.在电极上发生的反应如下： (谭青，李启厚，刘志宏，等.湿法炼锌过程中氟氯脱除技术 Zn2++2e→Zn↓ (4) 研究现状.湿法冶金，2015,34(4)：264) [5]Yu J.Yang H Y,Li L B,et al.Effects of fluoride and chloride on 2H++2e→H2↑ (5) zinc hydrometallurgical system and their removal methods.Nonfer- 从图7看出，此时各电极的析出电位分别为： rous Met (Extract Metall),2014(6):17 -1.4779(纯铝)、-1.4818、-1.4785、-1.4904、 (俞娟，杨洪英，李林波，等。全湿法炼锌系统中氟氯的影响 -1.4918、-1.4832和-1.4923V(0.3%Mn~ 及脱除方法.有色金属（冶炼部分），2014(6)：17) 2.0%Mn电极)，相比纯铝电极，含Mn电极分别增 [6]Bhatnagar A,Kumar E.Sillanpaa M.Fluoride removal from water by adsorption-a review.Chem Eng J,2011,171(3):811 加了3.9、0.6、1.25、1.39、5.3和14.4mV.可以得 [7]Gui Y,Luan X W.Effect of cerium on microstructure and corro- 出，添加Mn元素后电极的析出电位有增大的趋势， sion resistance of hot-dip galvanized zinc-aluminum-magnesium 随着Mn元素含量的增加，析出电位有增大的趋势， alloy coating.Electroplat Finish,2015,34(9):476 析出电位的增加与Mn元素在合金中的分布有关. (桂艳，栾向伟.铈元素对热浸锌-铝-镁合金镀层显微组织 综合考虑各种性能，含Mn质量分数1.5%的铝锰合 及耐蚀性的影响.电镀与涂饰，2015,34(9)：476) 金比较适合于锌电积用阴极. [8]Lins V F C,Castro MM R,Aratijo C R,et al.Effect of nickel and magnesium on zinc electrowinning using sulfate solutions.Bras 3结论 J Chem Eng,2011,28(3):475 [9]Zhang W,Robichaud M,Ghali E,et al.Electrochemical behavior (1)含有Mn元素的铝锰合金电极相比于纯铝 of mesh and plate oxide coated anodes during zinc electrowinning. 电极，耐蚀性普遍提高：随着Mn元素含量增加，腐 Trans Nonferrous Met Soci China,2016,26(2):589 蚀电流逐渐减小，在Mn质量分数1.5%时达最低 [10]Gu P,Pascual R,Shirkhanzadeh M,et al.The influence of Al (1.11mA·cm-2):腐蚀电位与Mn含量有关，无明显 substrate intermetallic precipitates on zine electrodeposition.Hy- 变化规律，Mn质量分数1.5%时值最小(-1.0954V). drometallurgy,1995.37(3):267 [11]Mackinnon D J,Brannen J M,Fenn P L.Characterization of im- (2)交换电流密度受Mn元素的影响明显，交换 purity effects in zinc electrowinning from industrial acid sulphate 电流密度随Mn含量增加呈现出先增加后减小趋 electrolyte.J Appl Electrochem,1987,17(6):1129 势，在Mn质量分数1.5%时达最大3.7462×10-16 [12]Gu P,Pascual R,Shirkhanzadeh M,et al.The influence of in- mA·cm-2,远大于纯铝电极(4.8027×10-3mA· termetallic precipitates on the adhesion of electrodeposited zine to cm-2);整体变化幅度明显，电极表面电催化提高， aluminum cathodes.Hydrometallurgy,1995,37(3):283 [13]Nusen S,Yottawee N,Daopiset S,et al.The role of surface 电流效率增加，能耗降低. grinding,intermetallic precipitates and halide ions on zine depo- (3)Mn元素的添加对电极的析氢过电位影响 sition and adhesion on aluminium cathode in zinc electrowinning. 较小，析氢过电位和纯铝电极整体相近，其中Mn质 Hydrometallurgy,2012,113-114:143工程科学学报,第 40 卷,第 7 期 图 7 不同质量分数 Mn 的铝合金电极的恒电流极化曲线 Fig. 7 Galvanostatic polarization of Al alloy electrodes with different Mn concentrations 要是电极在极化电流作用下,达到析出电位后不断 有金属离子的还原与晶核的生成,改变了电极表面 各点的平衡电势,但随着时间的延长,电极电压整体 趋于稳定平衡状态[20] . 在电极上发生的反应如下: Zn 2 + + 2e - 寅Zn引 (4) 2H + + 2e - 寅H2尹 (5) 从图 7 看出,此时各电极的析出电位分别为: - 1郾 4779 (纯铝)、 - 1郾 4818、 - 1郾 4785、 - 1郾 4904、 - 1郾 4918、 - 1郾 4832 和 - 1郾 4923 V ( 0郾 3% Mn ~ 2郾 0% Mn 电极),相比纯铝电极,含 Mn 电极分别增 加了 3郾 9、0郾 6、1郾 25、1郾 39、5郾 3 和 14郾 4 mV. 可以得 出,添加 Mn 元素后电极的析出电位有增大的趋势, 随着 Mn 元素含量的增加,析出电位有增大的趋势, 析出电位的增加与 Mn 元素在合金中的分布有关. 综合考虑各种性能,含 Mn 质量分数 1郾 5% 的铝锰合 金比较适合于锌电积用阴极. 3 结论 (1)含有 Mn 元素的铝锰合金电极相比于纯铝 电极,耐蚀性普遍提高;随着 Mn 元素含量增加,腐 蚀电流逐渐减小,在 Mn 质量分数 1郾 5% 时达最低 (1郾 11 mA·cm - 2 );腐蚀电位与 Mn 含量有关,无明显 变化规律,Mn 质量分数1郾 5%时值最小( -1郾 0954 V). (2)交换电流密度受 Mn 元素的影响明显,交换 电流密度随 Mn 含量增加呈现出先增加后减小趋 势,在 Mn 质量分数 1郾 5% 时达最大 3郾 7462 伊 10 - 16 mA·cm - 2 ,远大于纯铝电极 ( 4郾 8027 伊 10 - 33 mA· cm - 2 );整体变化幅度明显,电极表面电催化提高, 电流效率增加,能耗降低. (3)Mn 元素的添加对电极的析氢过电位影响 较小,析氢过电位和纯铝电极整体相近,其中 Mn 质 量分数 0郾 3% 和 0郾 9% 时,增加稍大(0郾 9472 V 和 0郾 9372 V),纯铝为 0郾 9077 V. 在 500 A·m - 2极化电 流密度下的析出电位几乎不受 Mn 元素添加的 影响. 参 考 文 献 [1] Ta俳ski T, Pakie覥a W, Janicki D, et al. Properties of the alumin鄄 ium alloy EN AC鄄鄄51100 after laser surface treatment. Arch Metall Mater, 2016, 61(1): 199 [2] Saleema N, Gallant D. Atmospheric pressure plasma oxidation of AA6061鄄鄄T6 aluminum alloy surface for strong and durable adhe鄄 sive bonding applications. Appl Surf Sci, 2013, 282: 98 [3] Lee H J, Yang I H, Kim S K, et al. In vivo comparison between the effects of chemically modified hydrophilic and anodically oxi鄄 dized titanium surfaces on initial bone healing. J Periodontal Im鄄 plant Sci, 2015, 45(3): 94 [4] Tan Q, Li Q H, Liu Z H, et al. Current situation on removal of fluorine and chlorine in zinc hydrometallurgy. Hydrometall China, 2015, 34(4): 264 (谭青, 李启厚, 刘志宏, 等. 湿法炼锌过程中氟氯脱除技术 研究现状. 湿法冶金, 2015, 34(4): 264) [5] Yu J, Yang H Y, Li L B, et al. Effects of fluoride and chloride on zinc hydrometallurgical system and their removal methods. Nonfer鄄 rous Met (Extract Metall), 2014(6): 17 (俞娟, 杨洪英, 李林波, 等. 全湿法炼锌系统中氟氯的影响 及脱除方法. 有色金属(冶炼部分), 2014(6): 17) [6] Bhatnagar A, Kumar E, Sillanp覿覿 M. Fluoride removal from water by adsorption———a review. Chem Eng J, 2011, 171(3): 811 [7] Gui Y, Luan X W. Effect of cerium on microstructure and corro鄄 sion resistance of hot鄄dip galvanized zinc鄄鄄 aluminum鄄鄄 magnesium alloy coating. Electroplat Finish, 2015, 34(9): 476 (桂艳, 栾向伟. 铈元素对热浸锌鄄鄄 铝鄄鄄 镁合金镀层显微组织 及耐蚀性的影响. 电镀与涂饰, 2015, 34(9): 476) [8] Lins V F C, Castro M M R, Ara俨jo C R, et al. Effect of nickel and magnesium on zinc electrowinning using sulfate solutions. Braz J Chem Eng, 2011, 28(3): 475 [9] Zhang W, Robichaud M, Ghali E, et al. Electrochemical behavior of mesh and plate oxide coated anodes during zinc electrowinning. Trans Nonferrous Met Soci China, 2016, 26(2): 589 [10] Gu P, Pascual R, Shirkhanzadeh M, et al. The influence of Al substrate intermetallic precipitates on zinc electrodeposition. Hy鄄 drometallurgy, 1995, 37(3): 267 [11] Mackinnon D J, Brannen J M, Fenn P L. Characterization of im鄄 purity effects in zinc electrowinning from industrial acid sulphate electrolyte. J Appl Electrochem, 1987, 17(6): 1129 [12] Gu P, Pascual R, Shirkhanzadeh M, et al. The influence of in鄄 termetallic precipitates on the adhesion of electrodeposited zinc to aluminum cathodes. Hydrometallurgy, 1995, 37(3): 283 [13] Nusen S, Yottawee N, Daopiset S, et al. The role of surface grinding, intermetallic precipitates and halide ions on zinc depo鄄 sition and adhesion on aluminium cathode in zinc electrowinning. Hydrometallurgy, 2012, 113鄄114: 143 ·806·