Effect of Organic Additives on Electrodeposition Behavior of Zn from Zincate Solution Containing Potassium Hydroxide and Its Micro Structure

K. Fukumoto, S. Oue, Tsukasa Niwa, Yoshiharu Kikuchi, S. Akamatsu, Hiroaki Nakano
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Abstract

Zn was electrodeposited on an Fe electrode at a current density of 50­5000A·m12, charge of 4 © 104C·m12, and temperature of 313K in an unagitated zincate solution containing 0.62mol·dm13 of ZnO, 4.0mol·dm13 of KOH or NaOH, and organic additives. The effects of KOH and NaOH on the deposition behavior of Zn in the solution containing the organic additives and on the microstructure of the deposits were investigated. In a solution containing a straight-chain polymer composed of a quaternary ammonium cation (PQ) and a quaternary ammonium salt with a benzene ring (QA), the current efficiency for Zn deposition in a high-current-density region (1000­5000A·m12) to produce glossy films was higher with KOH than that with NaOH. At high current densities above 1000A·m12, the Zn deposition approached the diffusion limitation of ZnO2 ions. With the addition of PQ and QA, the diffusion of ZnO2 ions was significantly suppressed, and the degree of suppression was smaller with KOH than that with NaOH. The polarization resistance at 200A·m12, which was investigated through alternating current impedance, revealed that the adsorption ability of PQ and QA onto the cathode was smaller with KOH than that with NaOH. Since the suppression effect of the additives on the Zn deposition was smaller with KOH than that with NaOH, the current efficiency for Zn deposition in the high-current-density region was larger with KOH. The upper limit of the current density needed to produce glossy films was smaller with KOH than that with NaOH, and spongy thin films were partially observed on platelet crystals obtained at high current densities in the KOH solution. The C content resulting from the additives in the deposited Zn was smaller with KOH because the adsorption ability of PQ and QA onto the cathode was smaller with KOH than that with NaOH. [doi:10.2320/matertrans.MT-M2021027]
有机添加剂对含氢氧化钾锌酸盐溶液中锌电沉积行为及其微观结构的影响
在含0.62mol·dm13 ZnO、4.0mol·dm13 KOH或NaOH和有机添加剂的未搅拌锌酸盐溶液中,以电流密度50 ~ 5000a·m12、电荷4©104C·m12、温度313K的Fe电极上电沉积Zn。研究了KOH和NaOH对Zn在含有机添加剂溶液中的沉积行为和镀层微观结构的影响。在含有季铵盐阳离子(PQ)和带苯环的季铵盐(QA)组成的直链聚合物溶液中,在高电流密度区(1000 ~ 5000a·m12), KOH沉积Zn的电流效率高于NaOH。在1000A·m12以上的高电流密度下,Zn沉积接近ZnO2离子的扩散极限。随着PQ和QA的加入,ZnO2离子的扩散受到明显抑制,且KOH的抑制程度小于NaOH。在200A·m12时,通过交流阻抗对PQ和QA在阴极上的吸附能力进行了研究,结果表明KOH对PQ和QA在阴极上的吸附能力比NaOH小。由于添加剂对KOH对Zn沉积的抑制作用比NaOH对Zn沉积的抑制作用小,因此KOH对Zn在高电流密度区域沉积的电流效率更大。在KOH溶液中产生光面膜所需的电流密度上限比在NaOH溶液中要小,在高电流密度的KOH溶液中获得的血小板晶体上部分观察到海绵状薄膜。由于PQ和QA在阴极上的吸附能力在KOH的作用下比在NaOH的作用下要小,所以KOH对沉积Zn中添加剂产生的C含量更小。(doi: 10.2320 / matertrans.MT-M2021027)
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