CoCrNi中熵合金在不同浓度NH4Cl溶液中的腐蚀行为研究

doi:10.11902/1005.4537.2023.177

中国腐蚀与防护学报

2024, Vol. 44

Issue (3): 725-734 CSTR: 32134.14.1005.4537.2023.177 DOI: 10.11902/1005.4537.2023.177

研究报告

本期目录 | 过刊浏览

CoCrNi中熵合金在不同浓度NH₄Cl溶液中的腐蚀行为研究

张成龙¹^,², 张斌¹, 朱敏¹(

), 袁永锋¹, 郭绍义¹, 尹思敏¹

1.浙江理工大学机械工程学院杭州 310018
2.北京中科科仪股份有限公司北京 100190

Corrosion Behavior of Medium Entropy CoCrNi-alloy in NH₄Cl Solutions

ZHANG Chenglong¹^,², ZHANG Bin¹, ZHU Min¹(

), YUAN Yongfeng¹, GUO Shaoyi¹, YIN Simin¹

1. School of Mechanical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China
2. Kyky Technology Co., Ltd., Beijing 100190, China

引用本文:

张成龙, 张斌, 朱敏, 袁永锋, 郭绍义, 尹思敏. CoCrNi中熵合金在不同浓度NH₄Cl溶液中的腐蚀行为研究[J]. 中国腐蚀与防护学报, 2024, 44(3): 725-734.
Chenglong ZHANG, Bin ZHANG, Min ZHU, Yongfeng YUAN, Shaoyi GUO, Simin YIN. Corrosion Behavior of Medium Entropy CoCrNi-alloy in NH₄Cl Solutions[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(3): 725-734.

全文: PDF(6523 KB) HTML

摘要:

通过电化学测试、统计学分析和浸泡腐蚀实验系统地研究了等原子CoCrNi中熵合金(MEA)在不同浓度NH₄Cl溶液中的腐蚀行为及机理。结果表明，随着NH₄Cl浓度的增加，MEA的腐蚀电位(E_corr)负移，维钝电流密度(I_p)增大，腐蚀速率增加，合金的耐腐蚀性能降低。当NH₄Cl浓度为3%和8%时，阳极曲线出现了明显的活化-钝化过渡区，意味着合金钝性降低。此外，随着NH₄Cl浓度的增加，MEA表面钝化膜的缺陷密度明显增加，钝化膜的厚度减薄，稳定性降低，这削弱了膜对合金的保护能力。NH₄⁺和Cl^-的共同作用促进了亚稳态点蚀的形核和发展，且在高浓度的NH₄Cl溶液中，亚稳态点蚀难以再钝化，容易发展为稳态点蚀。MEA腐蚀形态主要为点蚀。

关键词 ：中熵合金, 腐蚀行为, 亚稳态点蚀, 钝化膜

Abstract：

The corrosion behavior and mechanism of medium entropy equiatomic CoCrNi alloy (MEA) in various NH₄Cl solutions (i.e., with 1%, 3% and 8% NH₄Cl) were systematically studied by electrochemical test, statistical analysis, and immersion corrosion test. The results show that with the increase of NH₄Cl concentration, the corrosion potential (E_corr) of the MEA shifts negatively, the passive current density (I_p) increases, and the corrosion rate rises, indicating that the corrosion resistance of the alloy decreases. When the concentrations of NH₄Cl solution are 3% and 8%, the anodic polarization curve displays a clear active-passive transition zone, which means that the passivity of the MEA is reduced. In addition, as NH₄Cl concentration increases, the defect density within the passivation film on the MEA increases significantly, the thickness of the film decreases, and its stability declines, which weakens the protection ability of the film. The combined effect between NH₄⁺ and Cl^- promotes the nucleation and development of metastable pitting corrosion, while in the high concentration of NH₄Cl solution, the metastable pits are difficult to be re-passivated, and easy to develop into steady pits. In general, the main corrosion form of the MEA is pitting corrosion.

Key words： MEA corrosion behavior metastable pitting corrosion passive film

收稿日期: 2023-05-26 32134.14.1005.4537.2023.177

ZTFLH:

TG178

基金资助:浙江省自然科学基金(LY18E010004);浙江理工大学基本科研业务费(22242293-Y)

通讯作者: 朱敏，E-mail：zmii2009@163.com，研究方向为金属材料的腐蚀与防护

Corresponding author: ZHU Min, E-mail:zmii2009@163.com

作者简介: 张成龙，男，1996年生，硕士生

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图1 CoCrNi MEA的微观组织

图2 CoCrNi MEA在不同浓度NH4Cl溶液中的开路电位

图3 CoCrNi MEA在NH4Cl溶液中的动电位极化曲线

表 1 动电位极化曲线拟合结果

图4 CoCrNi MEA在NH4Cl溶液中的EIS曲线及等效拟合电路

表2 电化学阻抗谱拟合结果

图5 CoCrNi MEA在NH4Cl溶液中的Rf和Rct值

图6 CoCrNi MEA在NH4Cl溶液中形成钝化膜的Mott-Schottky曲线，载流子浓度及钝化膜厚度

图7 CoCrNi MEA在NH4Cl溶液中的循环动电位极化曲线和滞回环面积

图8 CoCrNi MEA在NH4Cl溶液中的电流-时间瞬态曲线

图9 CoCrNi MEA的亚稳态点蚀电流峰

图10 CoCrNi MEA在NH4Cl溶液中的亚稳态点蚀的平均数量密度，电流瞬态峰值和寿命

图11 CoCrNi MEA在8%NH4Cl溶液中浸泡后的亚稳态点蚀形貌

图12 MEA在NH4Cl溶液中的平均腐蚀速率

图13 CoCrNi MEA在不同浓度NH4Cl溶液中浸泡5 d后的表面腐蚀形貌

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