FeNiCoCrW0.2Al0.1 高熵合金在硫酸盐还原菌溶液环境下的腐蚀研究

doi:10.11902/1005.4537.2024.084

中国腐蚀与防护学报

2025, Vol. 45

Issue (2): 460-468 CSTR: 32134.14.1005.4537.2024.084 DOI: 10.11902/1005.4537.2024.084

研究报告

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FeNiCoCrW_0.2Al_0.1 高熵合金在硫酸盐还原菌溶液环境下的腐蚀研究

许竞翔¹, 黄睿阳¹, 褚振华¹(

), 蒋全通²(

)

^1.上海海洋大学工程学院上海 201306
^2.中国科学院海洋研究所海洋环境腐蚀与生物污损重点实验室青岛 266404

Corrosion Behavior of High Entropy Alloy FeNiCoCrW_0.2Al_0.1 in Sulfate-reducing Bacteria Containing Solution

XU Jingxiang¹, HUANG Ruiyang¹, CHU Zhenhua¹(

), JIANG Quantong²(

)

^1.College of Engineering Science and Technology, Shanghai Ocean University, Shanghai 201306, China
^2.CAS Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266404, China

引用本文:

许竞翔, 黄睿阳, 褚振华, 蒋全通. FeNiCoCrW_0.2Al_0.1 高熵合金在硫酸盐还原菌溶液环境下的腐蚀研究[J]. 中国腐蚀与防护学报, 2025, 45(2): 460-468.
Jingxiang XU, Ruiyang HUANG, Zhenhua CHU, Quantong JIANG. Corrosion Behavior of High Entropy Alloy FeNiCoCrW_0.2Al_0.1 in Sulfate-reducing Bacteria Containing Solution[J]. Journal of Chinese Society for Corrosion and protection, 2025, 45(2): 460-468.

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摘要:

探究海洋环境中硫酸盐还原菌(SRB)对自行设计的FeNiCoCrW_0.2Al_0.1高熵合金腐蚀作用的影响及其潜在的钝化膜形成机制，并在SRB溶液中对其腐蚀行为进行了系统实验观察，特别关注了钝化膜的形成过程。结果显示，在SRB溶液中，高熵合金的耐腐蚀性能出现降低，这一现象可能与SRB代谢产物的直接作用有关，这些代谢产物促进了生物膜的形成，并削弱了原有的钝化膜，导致合金的耐蚀性受损。基于阴极去极化理论，本研究提出了高熵合金在SRB溶液中钝化膜形成的可能机理，并深入分析了生物膜对合金钝化膜保护效能的影响。

关键词 ：高熵合金, 硫酸盐还原菌, 微生物腐蚀, 钝化膜, 生物膜

Abstract：

Marine corrosion has always been a major challenge constraining the effective development and utilization of marine resources, among which microbiologically influenced corrosion (MIC) occupies an extremely important position. As an emerging alloy material, high entropy alloys (HEAs) show significant potential in inhibiting MIC due to their unique high mixed entropy properties. Herein, a HEA FeNiCoCrW_0.2Al_0.1 was designed and prepared, and then its corrosion behavior in sulfate-reducing bacteria (SRB) containing solutions was assessed with particular attention to the process of passivation film formation. The results showed that the HEA formed a double-layered passivation film in SRB solution, and the main component of the outer layer was Cr₂O₃, which had strong protective properties. However, the corrosion resistance of the HEA in the SRB solution was reduced compared with that in the sterile medium. This phenomenon may be related to the biological activities of SRB and the direct effect of their metabolites, which promote biofilm formation and weaken the original passivation film, resulting in the impaired corrosion resistance of the alloy. Based on the theory of cathodic depolarization, a mechanism for the passivation film formation of HEAs in SRB solution was proposed, and the influence of biofilm on the protective efficacy of the passivation film on the alloy was further analyzed.

Key words： HEA SRB MIC passivation film biofilm

收稿日期: 2024-03-16 32134.14.1005.4537.2024.084

ZTFLH:

TG174

基金资助:国家自然科学基金(51872072);上海市自然科学基金(20ZR1424000)

通讯作者: 褚振华，E-mail：zhchu@shou.edu.cn，研究方向为海洋材料的腐蚀与防护;
蒋全通，E-mail：jiangquantong@qdio.ac.cn，研究方向为海洋新材料的腐蚀与防护

Corresponding author: CHU Zhenhua, E-mail: zhchu@shou.edu.cn;
JIANG Quantong, E-mail: jiangquantong@qdio.ac.cn

作者简介: 许竞翔，男，1985年生，博士，教授

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图1 FeNiCoCrW0.2Al0.1高熵合金微观形貌及XRD分析

图2 FeNiCoCrW0.2Al0.1高熵合金在SRB溶液中浸泡不同天数后的FM形貌

图3 FeNiCoCrW0.2Al0.1高熵合金试样在SRB溶液浸泡9和24 d后的SEM形貌以及去除生物膜和腐蚀产物后的SEM形貌

图4 高熵合金试样在SRB溶液中和无菌培养基溶液中的极化曲线

表1 电化学测试的腐蚀参数和估算腐蚀速率

图5 用于拟合试样在SRB溶液中浸泡后的EIS的等效电路

图6 高熵合金试样在SRB溶液中浸泡9和24 d后的EIS

表2 EIS拟合得到的电路元件参数以及估算的钝化膜厚度

图7 高熵合金在SRB溶液中浸泡24 d后表面处合金元素的XPS精细谱及峰拟合结果

图8 高熵合金在SRB溶液中浸泡24 d后距表面4 nm处合金元素的XPS精细谱及峰拟合结果

表3 检测到的7种元素的XPS峰位置及其对应的可能氧化态

图9 高熵合金试样在SRB溶液中浸泡时形成的表面钝化膜的组成元素及其相对分数与对应的氧化态

图10 FeNiCoCrW0.2Al0.1高熵合金在SRB溶液中形成钝化膜的机理示意图

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