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中国腐蚀与防护学报  2022, Vol. 42 Issue (3): 493-500    DOI: 10.11902/1005.4537.2021.126
  研究报告 本期目录 | 过刊浏览 |
Cl-与HSO3-对建筑用439不锈钢腐蚀行为的影响
陈昊1, 樊志彬2, 陈志坚1,3, 周学杰1,3(), 郑鹏华1,3, 吴军1,4
1.武汉材料保护研究所有限公司 武汉 430030
2.国网山东省电力公司电力科学研究院 济南 250001
3.武汉大气淡水环境材料腐蚀国家野外观测科学研究站 武汉 430030
4.新疆尉犁大气环境材料腐蚀国家野外观测科学研究站 尉犁 841500
Effect of Cl- and HSO3- on Corrosion Behavior of 439 Stainless Steel Used in Construction
CHEN Hao1, FAN Zhibin2, CHEN Zhijian1,3, ZHOU Xuejie1,3(), ZHENG Penghua1,3, WU Jun1,4
1.Wuhan Institute of Materials Protection Co. Ltd. , Wuhan 430030, China
2.State Grid Shandong Electric Power Research Institute, Jinan 250001, China
3.Wuhan Materials Corrosion National Observation and Research Station, Wuhan 430030, China
4.Yuli Materials Corrosion National Observation and Research Station, Yuli 841500, China
全文: PDF(3078 KB)   HTML
摘要: 

采用电化学实验，并结合X射线衍射、X射线光电子能谱、分子动力学模拟测试与分析，从宏观电化学角度分析了439不锈钢在不同腐蚀溶液中的腐蚀行为，从微观分子层次阐明了腐蚀过程相应机理。电化学实验结果表明，对比单一腐蚀离子环境，Cl-与HSO3-同时存在时会显著增加439不锈钢材料的腐蚀速率；分子动力学模拟结果表明，相对单一腐蚀离子体系，混合腐蚀离子体系中各腐蚀离子与钝化膜的吸附更紧密，扩散系数也显著提高。439不锈钢在含Cl-环境中的腐蚀速率会随Cl-浓度的增加而逐渐加快，但到达Cl-临界浓度后会逐渐降低；而当环境中同时存在Cl-和HSO3-时，439不锈钢的腐蚀被加速。
关键词 ： 439不锈钢,  钝化膜,  点蚀,  电化学实验,  分子动力学模拟    
Abstract：

The pitting corrosion behavior and mechanism of ferritic stainless steel 439 in various solutions with different concentration of anions Cl- and HSO3- was studied by means of electrochemical test, X-ray diffractometer, X-ray photoelectron spectroscopy, as well as molecular dynamics simulation. Electrochemical test results show that, the corrosion rate of 439 stainless steel will be significantly increased in solutions with simultaneous presence of Cl- and HSO3- rather than that in solutions containing only one of the two anions. The molecular dynamics simulation results show that, compared with solutions containing only one of the two anions, in solutions of the mixed anions the corrosive ions were adsorbed much strongly to the passive film, and their diffusion coefficient is also significantly improved. The corrosion rate of 439 stainless steel in Cl- containing solutions will gradually increase with the increase of Cl- concentration, whereas after reaching the critical point, the corrosion rate will gradually decrease. However, when Cl- and HSO3- co-exist in the solution, the corrosion of 439 stainless steel is accelerated.
Key words： 439 stainless steel    passivation film    pitting corrosion    electrochemical test    molecular dynamics simulation
收稿日期: 2021-06-07     
ZTFLH:  TG172.3  
基金资助:国家电网有限公司总部科技项目(5200-202016471A-0-0-00)
通讯作者: 周学杰     E-mail: zhouxj11@163.com
Corresponding author: ZHOU Xuejie     E-mail: zhouxj11@163.com
作者简介: 陈昊，男，1996年生，硕士，助理工程师
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引用本文:

陈昊, 樊志彬, 陈志坚, 周学杰, 郑鹏华, 吴军. Cl-与HSO3-对建筑用439不锈钢腐蚀行为的影响[J]. 中国腐蚀与防护学报, 2022, 42(3): 493-500.
Hao CHEN, Zhibin FAN, Zhijian CHEN, Xuejie ZHOU, Penghua ZHENG, Jun WU. Effect of Cl- and HSO3- on Corrosion Behavior of 439 Stainless Steel Used in Construction. Journal of Chinese Society for Corrosion and protection, 2022, 42(3): 493-500.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.126      或      https://www.jcscp.org/CN/Y2022/V42/I3/493

图1  439不锈钢在不同浓度NaCl溶液中的极化曲线，电化学阻抗图谱及拟合曲线模型
NaCl (aq)EcorrVIcorrμA·cm-2Pitting potential / VPassive areas VRsΩ·cm-2Q1F·cm-2n1R1Ω·cm-2Q2F·cm-2n2R2Ω·cm-2
3.5%-0.0710.1190.3200.23146.941.20×10-50.874.96×1041.93×10-50.654.05×105
6.0%-0.0990.1640.2860.26427.851.22×10-50.911.38×1042.09×10-50.643.67×105
10.0%-0.2180.5180.0920.19018.944.00×10-50.831.21×1045.73×10-50.401.24×105
14.0%-0.1750.5090.1830.23817.134.71×10-50.918.14×1032.74×10-50.662.13×105
18.0%-0.1400.2850.1600.18012.291.62×10-50.928.59×1032.52×10-50.612.71×105
表1  439不锈钢极化曲线及阻抗谱拟合参数
图2  439不锈钢在不同浓度NaHSO3溶液和NaCl、NaHSO3混合溶液中的循环极化曲线
Solution / mol·L-1Ecorr / VIcorr / μA·cm-2Eb / VEp / VEb-Ep / V
0.62 NaCl-0.0710.1190.320------
0.05 NaHSO3-0.0170.0670.7920.3320.460
0.10 NaHSO3-0.0730.1010.7790.3210.459
0.50 NaHSO3-0.0790.1470.6150.2270.388
(0.62+0.05) NaCl+NaHSO3-0.3580.938-0.189-0.490---
(0.62+0.10) NaCl+NaHSO3-0.2820.6130.258-0.491---
(0.62+0.50) NaCl+NaHSO3-0.3230.4050.424-0.444---
表2  循环极化曲线特征参数
图3  439不锈钢在不同浓度的NaHSO3和混合溶液中的电化学阻抗谱
Solution / (mol·L-1)Rs / Ω·cm-2Q1 / F·cm-2n1R1 / Ω·cm-2Q2 / F·cm-2n2R2 / Ω·cm-2
0.62 NaCl50.171.39×10-50.872.01×1044.08×10-50.652.07×105
0.05 NaHSO3485.701.82×10-50.914.01×1041.37×10-50.457.55×105
0.10 NaHSO3258.402.91×10-50.981.60×1042.81×10-50.753.09×105
0.50 NaHSO364.092.11×10-50.371.36×1042.52×10-50.902.95×105
(0.62+0.05) NaCl+NaHSO340.652.94×10-50.904.24×1032.98×10-50.822.48×104
(0.62+0.10) NaCl+NaHSO338.862.41×10-50.918.15×1033.37×10-50.603.21×104
(0.62+0.50) NaCl+NaHSO327.722.76×10-50.917.70×1033.87×10-50.723.34×104
表3  电化学阻抗谱等效电路拟合参数
图4  标准样表面X射线衍射谱图
图5  标准样表面X射线光电子能谱
图6  3种腐蚀体系及元素模型图
图7  分子动力学模拟试验平衡判据
Phase0.62 mol/L NaCl0.62 mol/L NaHSO3(0.31+0.31) mol/L (NaCl+NaHSO3)
Cl-HSO3-(Cl-, HSO3-)
Fe2O3-1323.182226-24.479770-1432.066031
Cr2O3-8789.661657-89.576001-7837.384689
FeO-2582.008070-3877.935214-11311.721163
表4  腐蚀离子与金属氧化物表面相互作用能
Phase3.5%NaCl0.62 mol/L NaHSO3(0.31+0.31) mol/L (NaCl+NaHSO3)
Cl-HSO3-Cl-HSO3-
Fe2O32.02×10-53.24×10-51.64×10-52.13×10-5
Cr2O35.86×10-102.23×10-54.32×10-82.82×10-5
FeO4.39×10-51.41×10-57.06×10-58.26×10-6
表5  腐蚀离子的扩散系数
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