<strong>5083-H111</strong>铝合金在模拟动态海水环境中的局部腐蚀机制

doi:10.11902/1005.4537.2023.140

中国腐蚀与防护学报

2023, Vol. 43

Issue (4): 683-692 CSTR: 32134.14.1005.4537.2023.140 DOI: 10.11902/1005.4537.2023.140

中国腐蚀与防护学会杰出青年成就奖论文专栏

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5083-H111铝合金在模拟动态海水环境中的局部腐蚀机制

邓成满¹^,², 刘喆¹^,², 夏大海¹^,²(

), 胡文彬¹^,²

^1.天津市材料复合与功能化重点实验室天津 300350
^2.天津大学材料科学与工程学院天津 300350

Localized Corrosion Mechanism of 5083-H111 Al Alloy in Simulated Dynamic Seawater Zone

DENG Chengman¹^,², LIU Zhe¹^,², XIA Da-Hai¹^,²(

), HU Wenbin¹^,²

^1.Tianjin Key Laboratory of Composite and Functional Materials, Tianjin 300350, China
^2.School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China

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摘要:

采用开路电位 (OCP)、电化学阻抗谱 (EIS)，并结合扫描电子显微镜 (SEM) 和X射线光电子能谱 (XPS) 技术，研究了5083-H111铝合金在模拟动态海水环境中的电化学行为，并探讨了局部腐蚀机制。5083-H111铝合金的金属间化合物以Al-Fe和Mg-Si相为主，点蚀主要分布于金属间化合物周围；Al-Fe相在腐蚀过程中充当阴极，与周围Al基体构成微腐蚀电池，促使Al基体的点蚀。Mg-Si相在腐蚀过程中最初充当阳极，当其发生选择性溶解导致脱合金化逐渐形成富Si相后，变为阴极，促使Al基体发生点蚀。5083-H111铝合金表面生成的腐蚀产物为Al(OH)₃、Al₂O₃和AlCl₃。腐蚀产物在腐蚀初期对Al基体起到良好的保护作用，导致OCP正移，极化电阻 (R_p) 增大；腐蚀后期 (36~56 d)，初始腐蚀产物会发生局部脱落，在脱落位置Al基体再次发生局部腐蚀，导致OCP负移，R_p急剧减小。随着暴露时间的延长，部分金属间化合物在腐蚀后期会发生脱落，形成腐蚀空腔。

关键词 ： 5083-H111铝合金, 动态海水环境, 局部腐蚀, 金属间化合物, 电化学阻抗谱

Abstract：

The localized corrosion of 5083-H111 Al alloy in a simulated dynamic seawater zone was investigated by open circuit potential (OCP) measurement, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results revealed that, in the simulated dynamic seawater, 5083-H111 Al alloy generated visible pitting corrosion caused by the intermetallic particles (IMPs). These IMPs were composed of Al-Fe phase and Mg-Si phase, Al-Fe phase acted as a cathode during the corrosion, forming a micro-corrosion cell with the surrounding Al matrix, accelerating the corrosion of the Al matrix. Mg-Si phase was firstly acted as anode, the selective dissolution of Mg in the Mg-Si particles results in a de-alloyed outer layer on the exposed surfaces and forms Si-containing phase, then the Si-containing phase acted as cathode, prompting pitting corrosion of Al matrix. The corrosion products generated on the surface of 5083-H111 Al alloy were Al(OH)₃, Al₂O₃·6H₂O and AlCl₃. These corrosion products provided a good protection to the Al matrix in the early stage of corrosion (1-36 d), resulting in a positive shift in OCP and an increase in the polarization resistance R_p. However, in the later stage of corrosion (36-56 d), the initial corrosion products were partially detached, leading to localized corrosion again at the detachment position, resulting in a negative shift of OCP and a sharp decrease in R_p. Finally, with the prolongation of exposed time, some IMPs detached from the corrosion pits, forming corrosion cavities.

Key words： 5083-H111 Al alloy dynamic seawater zone localized corrosion intermetallic particles electrochemical impedance spectroscopy

收稿日期: 2023-05-06 32134.14.1005.4537.2023.140

ZTFLH:

O646

基金资助:国家自然科学基金(52171077)

通讯作者: 夏大海，E-mail: dahaixia@tju.edu.cn，研究方向为腐蚀电化学

Corresponding author: XIA Da-Hai, E-mail: dahaixia@tju.edu.cn

作者简介: 邓成满，男，1998年生，硕士生
夏大海，1984 年出生，2012 年毕业于天津大学，获博士学位。现就职于天津大学，副教授、硕士研究生导师。主要研究方向为腐蚀电化学。承担国家自然科学基金面上项目和青年项目、“十三五”装备预研国防科技重点实验室基金等多项课题。现任中国腐蚀与防护学会第十一届理事、中国腐蚀与防护学会青年工作委员会委员、中国腐蚀与防护学会腐蚀电化学及测试方法委员会委员。已在Electrochim. Acta、J. Electrochem. Soc.、Corros. Sci. 等国内外学术刊物上发表SCI 论文150 余篇，H因子30。荣获天津市科技进步二等奖、2020-2021 年度天津市工程专业学位硕士研究生优秀论文指导教师、天津大学沈志康奖教金。目前担任Anti-Corrosion Methods and Materials 期刊副主编、Corrosion Communications 期刊Associate editor、《中国腐蚀与防护学报》编委、《中国有色金属学报》中、英文版和《装备环境工程》等期刊的青年编委。2023 年获得中国腐蚀与防护学会杰出青年学术成就奖。

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引用本文:

邓成满, 刘喆, 夏大海, 胡文彬. 5083-H111铝合金在模拟动态海水环境中的局部腐蚀机制[J]. 中国腐蚀与防护学报, 2023, 43(4): 683-692.
DENG Chengman, LIU Zhe, XIA Da-Hai, HU Wenbin. Localized Corrosion Mechanism of 5083-H111 Al Alloy in Simulated Dynamic Seawater Zone. Journal of Chinese Society for Corrosion and protection, 2023, 43(4): 683-692.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2023.140 或 https://www.jcscp.org/CN/Y2023/V43/I4/683

图1 5083-H111铝合金暴露在模拟动态海水环境36和56 d的微观腐蚀形貌

图2 5083-H111铝合金暴露在模拟动态海水环境56 d后由金属间化合物引起的点蚀

图3 5083-H111铝合金暴露在动态海水环境56 d后金属间化合物的微观形貌及元素分布

图4 5083-H111铝合金在动态海水环境暴露56 d后去除腐蚀产物的微观形貌

图5 5083-H111铝合金在动态海水环境中暴露56 d后金属间化合物的脱落

图6 5083-H111铝合金在动态海水环境中暴露56 d生成的腐蚀产物膜

图7 5083-H111铝合金暴露在动态海水环境56 d生成的腐蚀产物的微观结构

图8 5083-H111铝合金在模拟动态海水环境中暴露56 d后表面生成的腐蚀产物的XPS结果

图9 5083-H111铝合金在模拟动态海水环境中的OCP

图10 5083-H111铝合金在模拟动态海水环境的EIS

图11 拟合EIS数据的等效电路图

Time d	CPE_f		R_f10³ Ω⸱cm²	CPE_dl		R_ct10⁴ Ω⸱cm²	R_p10⁴ Ω⸱cm²	∑χ²
Time d	Q_f / 10^-6Ω^-1⸱cm^-2⸱s $n f$	n_f	R_f10³ Ω⸱cm²	Q_dl / 10^-6Ω^-1⸱cm^-2⸱s $n d l$	n_dl	R_ct10⁴ Ω⸱cm²	R_p10⁴ Ω⸱cm²	∑χ²
1	2.061	0.865	1.283	4.436	0.897	7.346	7.474	2.705×10^-2
16	11.42	0.894	0.721	10.731	0.919	9.398	9.471	2.029×10^-3
36	2.436	0.933	1.116	10.672	0.855	9.605	9.717	2.866×10^-2
56	1.981	0.987	0.413	9.570	0.840	6.216	6.257	4.264×10^-2

表1 基于电化学等效电路的EIS拟合参数

图12 5083-H111铝合金在模拟动态海水环境中的局部腐蚀机制示意图

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