<strong>2024</strong>铝合金表面<strong>PEDOT</strong>涂层的电化学制备及耐腐蚀性能

doi:10.11900/0412.1961.2020.00089

金属学报

2020, Vol. 56

Issue (11): 1541-1550 DOI: 10.11900/0412.1961.2020.00089

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2024铝合金表面PEDOT涂层的电化学制备及耐腐蚀性能

高博文¹^,², 王美涵¹(

), 闫茂成²(

), 赵洪涛², 魏英华², 雷浩²

1 沈阳大学机械工程学院沈阳 110044
2 中国科学院金属研究所沈阳 110016

Electrochemical Preparation and Corrosion Resistance of PEDOT Coatings on Surface of 2024 Aluminum Alloy

GAO Bowen¹^,², WANG Meihan¹(

), YAN Maocheng²(

), ZHAO Hongtao², WEI Yinghua², LEI Hao²

1 School of Mechanical Engineering, Shenyang University, Shenyang 110044, China
2 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

高博文, 王美涵, 闫茂成, 赵洪涛, 魏英华, 雷浩. 2024铝合金表面PEDOT涂层的电化学制备及耐腐蚀性能[J]. 金属学报, 2020, 56(11): 1541-1550.
Bowen GAO, Meihan WANG, Maocheng YAN, Hongtao ZHAO, Yinghua WEI, Hao LEI. Electrochemical Preparation and Corrosion Resistance of PEDOT Coatings on Surface of 2024 Aluminum Alloy[J]. Acta Metall Sin, 2020, 56(11): 1541-1550.

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摘要:

分别采用循环伏安法和恒电流法在2024铝合金基底上电沉积聚3,4-乙烯二氧噻吩(PEDOT)涂层，考察在3种电解质溶液(高氯酸锂(LiClO₄)和十二烷基硫酸钠(SDS)水溶液，邻苯二甲酸氢钠(C₈H₅NaO₄)和SDS水溶液，六氟磷酸四丁铵(TBAPF₆)乙腈溶液)中聚合3,4-乙烯二氧噻吩(EDOT)对PEDOT涂层生长和形貌的影响。通过电偶腐蚀、电化学阻抗谱(EIS)和扫描振动电极技术(SVET)研究PEDOT涂层与铝合金基底之间的相互作用。结果表明，TBAPF₆不仅对基底具有钝化和缓蚀作用，而且能够显著降低EDOT的氧化电位。恒电流法制备的涂层表面呈球状团聚且完整致密。电偶腐蚀和EIS结果表明，PEDOT涂层阻隔了腐蚀介质并使基底钝化，其阻值在DHS溶液(3.5 g/L (NH₄)₂SO₂+0.5 g/L NaCl)中浸泡3 d后达到最大。SVET结果表明，破损的PEDOT涂层能够促进表面电荷离域，避免电荷集中，产生电化学保护效应。

关键词 ： PEDOT涂层, 2024铝合金, 电沉积, EIS, SVET

Abstract：

Poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most promising anticorrosive materials due to its outstanding conductivity, stability, and environmental compatibility. From the standpoint of corrosion protection of aluminum alloys, PEDOT coatings are a good substitute for the traditional toxic chromium-based coatings. Electrochemical deposition, as a convenient and clean synthesis approach, has been widely employed for direct preparation of PEDOT coatings. Herein, cyclic voltammetry and constant-current method were used to electrodeposit PEDOT coatings on 2024 aluminum alloy substrates. The effects of polymerizing 3,4-ethylenedioxythiophene (EDOT) in three electrolyte solutions (lithium perchlorate (LiClO₄) and sodium dodecyl sulfate (SDS), sodium hydrogen phthalate (C₈H₅NaO₄) and SDS, and tetrabutylammonium hexafluorophosphate (TBAPF₆) acetonitrile) on the growth and morphology of the PEDOT coatings were investigated. The interactions between the coating and the aluminum substrate were studied through galvanic corrosion, electrochemical impedance spectra (EIS), and scanning vibration electrode technology (SVET). The results show that TBAPF₆ exhibited passivation and corrosion-inhibition effects on the substrate and significantly reduced the oxidation potential of EDOT. The surface morphology of the coating prepared via constant-current method showed complete and dense agglomerated spherical particles. The PEDOT coating formed a passivation layer on the substrate, and thus protected it from the corrosive medium. The maximum resistance was achieved in DHS solution (3.5 g/L (NH₄)₂SO₂+0.5 g/L NaCl) after 3 d. The scratched PEDOT coating could promote surface charge delocalization and avoid charge concentration, resulting in electrochemical protection of the aluminum alloy.

Key words： PEDOT coating 2024 aluminum alloy electrodeposition EIS SVET

收稿日期: 2020-03-19

ZTFLH:

TG178

基金资助:国家自然科学基金项目(52071320);国家重点基础研究发展计划项目(2014CB643304);中国科学院A类战略性先导科技专项项目(XDA13040500);辽宁省高等学校创新人才支持计划项目(LR2019044)

作者简介: 高博文，男，1994年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00089 或 https://www.ams.org.cn/CN/Y2020/V56/I11/1541

表1 3种电解质溶液成分和3,4-乙烯二氧噻吩(EDOT)单体加入量

图1 在不同电解质溶液中电聚合EDOT制备聚3,4-乙烯二氧噻吩(PEDOT)涂层的循环伏安曲线及涂层宏观形貌

图2 在不同电解质溶液中电聚合EDOT制备PEDOT涂层的恒电位曲线及涂层宏观形貌

图3 在不同电解质溶液中恒电流电聚合EDOT制备PEDOT涂层的SEM像

图4 在DHS溶液(3.5 g/L (NH4)2SO2+0.5 g/L NaCl)中PEDOT/2024铝合金电极与2024铝合金电极偶接时的电位(E)和电流密度(i)

图5 在DHS溶液中2024铝合金电极和PEDOT/2024铝合金电极的EIS

图6 浸泡电极的等效电路图

图7 PEDOT/2024铝合金电极划痕处在DHS溶液中浸泡不同时间的扫描振动电极(SVET)电流密度分布图

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