铜绿假单胞菌对<strong>CrCoNi</strong>中熵合金微生物腐蚀行为的影响

doi:10.11900/0412.1961.2019.00030

金属学报

2019, Vol. 55

Issue (11): 1457-1468 DOI: 10.11900/0412.1961.2019.00030

研究论文

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铜绿假单胞菌对CrCoNi中熵合金微生物腐蚀行为的影响

冯浩¹,李花兵¹(

),路鹏冲¹,杨纯田²,姜周华¹,武晓雷³

1. 东北大学冶金学院沈阳 110819
2. 沈阳材料科学国家研究中心东北大学联合研究分部沈阳 110819
3. 中国科学院力学研究所非线性力学国家重点实验室北京 100190

Investigation on Microbiologically Influenced Corrosion Behavior of CrCoNi Medium-Entropy Alloy byPseudomonas Aeruginosa

FENG Hao¹,LI Huabing¹(

),LU Pengchong¹,YANG Chuntian²,JIANG Zhouhua¹,WU Xiaolei³

1. School of Metallurgy, Northeastern University, Shenyang 110819, China
2. Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China
3. State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, China

引用本文:

冯浩,李花兵,路鹏冲,杨纯田,姜周华,武晓雷. 铜绿假单胞菌对CrCoNi中熵合金微生物腐蚀行为的影响[J]. 金属学报, 2019, 55(11): 1457-1468.
Hao FENG, Huabing LI, Pengchong LU, Chuntian YANG, Zhouhua JIANG, Xiaolei WU. Investigation on Microbiologically Influenced Corrosion Behavior of CrCoNi Medium-Entropy Alloy byPseudomonas Aeruginosa[J]. Acta Metall Sin, 2019, 55(11): 1457-1468.

全文: PDF(18001 KB) HTML

摘要:

采用多种电化学实验手段及场发射扫描电子显微镜(FESEM)、激光共聚焦扫描显微镜(CLSM)等分析技术，结合活死细菌染色实验、点蚀坑深度分析等方法，以316L不锈钢为对比，研究了CrCoNi中熵合金在含铜绿假单胞菌培养基中的微生物腐蚀行为。结果表明：铜绿假单胞菌能够在CrCoNi中熵合金表面形成不均匀的生物被膜，从而降低开路电位，减小极化电阻和电荷转移电阻，增大腐蚀电流密度；铜绿假单胞菌生物被膜在一定程度上破坏了钝化膜，导致浸泡在含铜绿假单胞菌培养基中的CrCoNi中熵合金的最大点蚀坑深度(4.8 μm)大于无菌培养基中CrCoNi中熵合金的最大点蚀坑深度(2.3 μm)。与316L不锈钢相比，CrCoNi中熵合金的开路电位较高，腐蚀电流密度和腐蚀速率较小，钝化膜的修复能力较强，在含铜绿假单胞菌培养基中浸泡后的最大点蚀坑深度小于316L不锈钢(5.8 μm)。

关键词 ： CrCoNi中熵合金, 铜绿假单胞菌, 微生物腐蚀, 生物被膜, 点蚀

Abstract：

The CrCoNi medium-entropy alloy (MEA) has excellent strength and toughness, and can be used as the basis for the development of promising engineering alloys in the future. However, microbiologically influenced corrosion (MIC) of CrCoNi MEA has rarely been reported. Especially, pseudomonas aeruginosa (P. aeruginosa) is the typical bacteria associated with MIC, which is widely distributed in the ocean and soil. It can form biofilm on the surface of steel and accelerate the corrosion of carbon steels and stainless steels (SSs). In this study, the electrochemical experiments such as open current potential (OCP), linear polarization resistance (LPR), electrochemical frequency modulation (EFM), electrochemical impedance spectroscopy (EIS) and cyclic polarization (CP) were used to investigate the MIC behavior of CrCoNi MEA caused by P. aeruginosa, in comparison with 316L SS. Surface analysis techniques such as FESEM and CLSM were used to observe the P. aeruginosa biofilm and pitting morphology on the coupon surface. The results show that P. aeruginosa could form an uneven biofilm on the surface of CrCoNi MEA coupons. The P. aeruginosa accelerated the corrosion rate of CrCoNi MEA, which was demonstrated by a negative shift of open circuit potential, a decrease of polarization resistance and charge transfer resistance, and an increase of corrosion current density in P. aeruginosa medium. The P. aeruginosa biofilm could destroy the passive film of the CrCoNi MEA coupons, which led to the maximum pit depth of the coupons exposed in P. aeruginosa medium (4.8 μm) for 14 d much deeper than that in sterile medium (2.3 μm). Compared with 316L SS, CrCoNi had higher open circuit potential, lower corrosion current density and corrosion rate, and higher repairability of passive film. Meanwhile, the maximum pit depth on the CrCoNi MEA coupons in P. aeruginosa medium was shallower than that of 316L SS (5.8 μm).

Key words： CrCoNi medium-entropy alloy (MEA) pseudomonas aeruginosa microbiologically influenced corrosion (MIC) biofilm pitting corrosion

收稿日期: 2019-01-29

ZTFLH:

TG178

基金资助:国家自然科学基金项目Nos(51434004);国家自然科学基金项目Nos(51774074);国家自然科学基金项目Nos(U1435205);国家自然科学基金项目Nos(51434004、51774074和U1435205);中央高校基本科研业务费专项基金项目No(N172512033);以及沈阳市重大科技成果转化项目No(Z17-5-003)

作者简介: 冯浩，男，1992年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2019.00030 或 https://www.ams.org.cn/CN/Y2019/V55/I11/1457

表1 CrCoNi中熵合金及316L不锈钢的化学成分 (mass fraction / %)

图1 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中的开路电位(EOCP)、线性极化电阻的倒数(1/Rp)和腐蚀速率随时间的变化规律

图2 无菌及含铜绿假单胞菌培养基在14 d内的pH值变化曲线

图3 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡不同时间的Nyquist图和Bode图

图4 电化学阻抗谱(EIS)等效电路图

表2 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中EIS拟合参数

图5 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡7和14 d后的循环极化曲线

表3 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡7 d的循环极化曲线参数

图6 CrCoNi中熵合金与316L不锈钢在含铜绿假单胞菌培养基中浸泡14 d并进行循环极化后的宏观形貌

图7 CrCoNi中熵合金及316L不锈钢在含铜绿假单胞菌培养基中浸泡7 d后的FESEM和CLSM像

图8 CrCoNi中熵合金及316L不锈钢在含铜绿假单胞菌培养基中浸泡14 d后的FESEM和CLSM像

图9 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后最大点蚀坑的CLSM像

表5 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后的点蚀坑深度 (μm)

图10 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后点蚀坑深度的累积概率

图11 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后点蚀坑深度的Gumbel分布

表4 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d的循环极化曲线参数

表6 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后的Gumbel分布参数

图12 CrCoNi中熵合金与316L不锈钢在无菌及含铜绿假单胞菌培养基中浸泡14 d后形成稳态点蚀的概率分布

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