2024铝合金表面PEDOT涂层的电化学制备及耐腐蚀性能
收稿日期: 2020-03-19
修回日期: 2020-06-05
网络出版日期: 2020-08-18
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)
Electrochemical Preparation and Corrosion Resistance of PEDOT Coatings on Surface of 2024 Aluminum Alloy
Received date: 2020-03-19
Revised date: 2020-06-05
Online published: 2020-08-18
Supported by
National Natural Science Foundation of China(52071320);National Basic Research Program of China(2014CB643304);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA13040500);Program for Innovation Talents in Univerisity of Liaoning Province(LR2019044)
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。
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 . DOI: 10.11900/0412.1961.2020.00089
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
| [1] | Dudoladov A O, Buryakovskaya O A, Vlaskin M S, et al. Generation of hydrogen by aluminium oxidation in aquaeous solutions at low temperatures [J]. Int. J. Hydrogen Energy, 2016, 41: 2230 |
| [2] | Zhang X F, Fu C R, Xia Y J, et al. Atomistic origin of the complex morphological evolution of aluminum nanoparticles during oxidation: A chain-like oxide nucleation and growth mechanism [J]. ACS Nano, 2019, 13: 3005 |
| [3] | Gao L, Yue R R, Xu J K, et al. Pt-PEDOT/rGO nanocomposites: One-pot preparation and superior electrochemical sensing performance for caffeic acid in tea [J]. J. Electroanal. Chem., 2018, 816: 14 |
| [4] | Li M R, Wang W, Chen Z, et al. Electrochemical determination of paracetamol based on Au@graphene core-shell nanoparticles doped conducting polymer PEDOT nanocomposite [J]. Sens. Actuators, 2018, 260B: 778 |
| [5] | Aguirre J, Daille L, Fischer D A, et al. Study of poly(3,4-ethylendioxythiphene) as a coating for mitigation of biocorrosion of AISI 304 stainless steel in natural seawater [J]. Prog. Org. Coat., 2017, 113: 175 |
| [6] | Hou J, Zhu G, Xu J K, et al. Anticorrosion performance of epoxy coatings containing small amount of inherently conducting PEDOT/PSS on hull steel in seawater [J]. J. Mater. Sci. Technol., 2013, 29: 678 |
| [7] | Branzoi V, Pilan L, Golgovici F, et al. Electrochemical activity and corrosion protection properties of doped polypyrrole electrodeposited at pure aluminium electrode [J]. Mol. Cryst. Liq. Cryst., 2006, 446: 305 |
| [8] | Cheung K M, Bloor D, Stevens G C. Characterization of polypyrrole electropolymerized on different electrodes [J]. Polymer, 1988, 29: 1709 |
| [9] | Zhu G, Hou J, Zhu H F, et al. Electrochemical synthesis of poly(3,4-ethylenedioxythiophene) on stainless steel and its corrosion inhibition performance [J]. J. Coat. Technol. Res., 2013, 10: 659 |
| [10] | Kumar A M, Hussein M A, Adesina A Y, et al. Influence of surface treatment on PEDOT coatings: Surface and electrochemical corrosion aspects of newly developed Ti alloy [J]. RSC Adv., 2018, 8: 19181 |
| [11] | Lazzaroni R, Brédas J L, Dannetun P, et al. The chemical and electronic structure of the interface between aluminum and conjugated polymers [J]. Electrochim. Acta, 1994, 39: 235 |
| [12] | Gustafsson H, Kvarnstr?m C, Ivaska A. Comparative study of n-doping and p-doping of poly(3,4-ethylenedioxythiophene) electrosynthesised on aluminium [J]. Thin Solid Films, 2008, 517: 474 |
| [13] | Bantikassegn W, Ingan?s O. Electronic properties of junctions between aluminum and doped poly (3,4-ethylenedioxythiophene) [J]. Thin Solid Films, 1997, 293: 138 |
| [14] | Duan C H, Willems R E M, van Franeker J J, et al. Effect of side chain length on the charge transport, morphology, and photovoltaic performance of conjugated polymers in bulk heterojunction solar cells [J]. J. Mater. Chem., 2016, 4: 1855 |
| [15] | Hwang J, Amy F, Kahn A. Spectroscopic study on sputtered PEDOT·PSS: Role of surface PSS layer [J]. Org. Electron., 2006, 7: 387 |
| [16] | Yang Q, Yu S W, Fu P, et al. Boosting performance of non-fullerene organic solar cells by 2D g-C3N4 doped PEDOT:PSS [J]. Adv. Funct. Mater., 2020, 30: 1910205 |
| [17] | Song I S, Heo S W, Lee J Y, et al. Study on the ClO4 doped PEDOT-PEG in organic solvent using a hole injection layer for PLEDs [J]. J. Ind. Eng. Chem., 2011, 17: 651 |
| [18] | Del-Oso J A, Frontana-Uribe B A, Maldonado J L, et al. Electrochemical deposition of poly[ethylene-dioxythiophene] (PEDOT) films on ITO electrodes for organic photovoltaic cells: Control of morphology, thickness, and electronic properties [J]. J. Solid State Electrochem., 2018, 22: 2025 |
| [19] | Adamczyk L, Kulesza P J. Fabrication of composite coatings of 4-(pyrrole-1-yl) benzoate-modified poly-3,4-ethylenedioxythiophene with phosphomolybdate and their application in corrosion protection [J]. Electrochim. Acta, 2011, 56: 3649 |
| [20] | Hülser P, Beck F. Electrodeposition of polypyrrole layers on aluminium from aqueous electrolytes [J]. J. Appl. Electrochem., 1990, 20: 596 |
| [21] | Patra S, Barai K, Munichandraiah N. Scanning electron microscopy studies of PEDOT prepared by various electrochemical routes [J]. Synth. Met., 2008, 158: 430 |
| [22] | Martins J I, Costa S C, Bazzaoui M, et al. Conditions to prepare PPy/Al2O3/Al used as a solid-state capacitor from aqueous malic solutions [J]. J. Power Sources, 2006, 160: 1471 |
| [23] | Sakmeche N, Aaron J J, Aeiyach S, et al. Usefulness of aqueous anionic micellar media for electrodeposition of poly-(3,4-ethylenedioxythiophene) films on iron, mild steel and aluminium [J]. Electrochim. Acta, 2000, 45: 1921 |
| [24] | Sundfors F, Gustafsson H, Ivaska A, et al. Characterisation of the aluminium-electropolymerised poly(3,4-ethylenedioxythiophene) system [J]. J. Solid State Electrochem., 2010, 14: 1185 |
| [25] | Mansfeld F, Jeanjaquet S L, Kendig M W. An electrochemical impedance spectroscopy study of reactions at the metal/coating interface [J]. Corros. Sci., 1986, 26: 735 |
| [26] | Anothumakkool B, Soni R, Bhange S N, et al. Novel scalable synthesis of highly conducting and robust PEDOT paper for a high performance flexible solid supercapacitor [J]. Energy Environ. Sci., 2015, 8: 1339 |
| [27] | Groenendaal L, Jonas F, Freitag D, et al. Poly(3,4-ethylenedioxythiophene) and its derivatives: Past, present, and future [J]. Adv. Mater., 2000, 12: 481 |
| [28] | Malik M A, W?odarczyk R, Kulesza P J, et al. Protective properties of hexacyanoferrate containing polypyrrole films on stainless steel [J]. Corros. Sci., 2005, 47: 771 |
| [29] | Vempati S, Ertas Y, Celebioglu A, et al. Tuning the degree of oxidation and electron delocalization of poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) with solid-electrolyte [J]. Appl. Surf. Sci., 2017, 419: 770 |
| [30] | Prabakar S J R, Pyo M. Corrosion protection of aluminum in LiPF6 by poly(3,4-ethylenedioxythiophene) nanosphere-coated multiwalled carbon nanotube [J]. Corros. Sci., 2012, 57: 42 |
| [31] | Yan M C, Tallman D E, Rasmussen S C, et al. Corrosion control coatings for aluminum alloys based on neutral and n-doped conjugated polymers [J]. J. Electrochem. Soc., 2009, 156: C360 |
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