弹性拉应力下<strong>Q235</strong>碳钢在<strong>5%NaCl</strong>盐雾中的成锈行为及其机理

doi:10.11900/0412.1961.2021.00250

金属学报

2023, Vol. 59

Issue (6): 829-840 DOI: 10.11900/0412.1961.2021.00250

研究论文

本期目录 | 过刊浏览

弹性拉应力下Q235碳钢在5%NaCl盐雾中的成锈行为及其机理

李谦, 刘凯, 赵天亮(

)

上海大学材料科学与工程学院省部共建高品质特殊钢冶金与制备国家重点实验室上海 200444

Rust Formation Behavior and Mechanism of Q235 Carbon Steel in 5%NaCl Salt Spray Under Elastic Tensile Stress

LI Qian, LIU Kai, ZHAO Tianliang(

)

State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China

引用本文:

李谦, 刘凯, 赵天亮. 弹性拉应力下Q235碳钢在5%NaCl盐雾中的成锈行为及其机理[J]. 金属学报, 2023, 59(6): 829-840.
Qian LI, Kai LIU, Tianliang ZHAO. Rust Formation Behavior and Mechanism of Q235 Carbon Steel in 5%NaCl Salt Spray Under Elastic Tensile Stress[J]. Acta Metall Sin, 2023, 59(6): 829-840.

全文: PDF(3122 KB) HTML

摘要:

结合中性盐雾实验和四点弯曲法研究Q235碳钢在弹性拉应力作用下的预腐蚀成锈行为，采用SEM、XRD和电化学阻抗谱等手段研究了锈层的成分、结构以及电化学特性。结果表明，弹性拉应力通过加速阳极溶解促进锈层中γ-FeOOH物相的生成，且由于γ-FeOOH是在液相中生成，而γ-FeOOH向α-FeOOH和Fe₃O₄/γ-Fe₂O₃转化是在固-液界面进行，γ-FeOOH的生成速率比其转化速率快，导致锈层中γ-FeOOH的质量分数随应力水平提高而增加，α-FeOOH和Fe₃O₄/γ-Fe₂O₃的质量分数相应减少。随着应力由0增大至0.95σ_s (σ_s为屈服强度)，Fe₃O₄/γ-Fe₂O₃的质量分数由53%减小至约46%，α-FeOOH的质量分数由约30%减小至约23%，γ-FeOOH的质量分数由不到17%增大至约31%，这种物相成分变化导致锈层的致密性降低，厚度增加。此外，弹性拉应力通过加速阳极溶解促进了锈层的生长，进一步增加了锈层的厚度。锈层的厚度增加提高了离子在锈层中电迁移的阻力，锈层的致密性降低减弱了锈层内侧微环境的闭塞性，2者的共同作用使得锈层的保护性随应力水平的提高呈增强趋势。

关键词 ：弹性拉应力, 碳钢, 物相成分, 结构, 保护机制

Abstract：

As a structural steel material, carbon steel bears a certain extent of elastic tensile stress in actual service. Elastic tensile stress on steel is supposed to impact the electrochemical process and corrosion behavior, which may further influence the rusting behavior and the phase composition and structure of the formed rust layer. However, stresses on the steel substrate slightly influence the rust layer of carbon steel because no intrinsic change exists in the corrosion mechanism. Here, a remarkable effect of elastic tensile stress on Q235 carbon steel was found on the phase composition and structure of the rust layer formed in 5%NaCl salt spray. The effect on the rust layer was studied using SEM, XRD, and electrochemical impedance spectroscopy. The neutral salt spray test with four-point bending was used to preform the rust layer of Q235 steel under various stress levels. The results show that the elastic tensile stress accelerates the anodic dissolution, thereby promoting the generation of γ-FeOOH, which occurs faster in the electrolyte than the transformation of γ-FeOOH to α-FeOOH and Fe₃O₄/γ-Fe₂O₃ in the solid-liquid interface. Consequently, the mass fraction of γ-FeOOH in the rust layer increases as the stress level increases, whereas the mass fraction of α-FeOOH and Fe₃O₄/γ-Fe₂O₃ decreases accordingly. As the stress increases from 0 to 0.95σ_s (σ_s is yield strength), the mass fraction of Fe₃O₄/γ-Fe₂O₃ decreases from 53% to ~46%, the mass fraction of α-FeOOH decreases from ~30% to ~23%, and the mass fraction of γ-FeOOH increases from less than 17% to ~31%. Meanwhile, the phase composition change decreases the density and increases the thickness of the rust layer. Additionally, the acceleration of the anodic dissolution induced by the elastic tensile stress promotes the growth of the rust layer, which further increases the thickness of the rust layer. The increase in thickness and decrease in compactness of the rust layer jointly enhance the protective capability of the rust layer. The former increases the resistance to the electromigration of ions through the rust layer, and the latter mitigates the occlusion effect under the rust layer.

Key words： elastic tensile stress carbon steel phase composition structure protection mechanism

收稿日期: 2021-06-18

ZTFLH:

TG172.3

基金资助:国家重点研发计划项目(2017YFB0702100);上海市青年科技英才扬帆计划项目(20YF1412900)

通讯作者: 赵天亮，tlzhao@shu.edu.com，主要从事钢铁材料腐蚀和应力腐蚀行为研究

Corresponding author: ZHAO Tianliang, associate professor, Tel:15090998966, E-mail: tlzhao@shu.edu.com

作者简介: 李谦，男，1975年生，教授

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图1 四点弯曲加载装置示意图

图2 不同弹性拉应力水平下Q235碳钢在5%NaCl盐雾中的质量损失随时间的变化

表1 不同弹性拉应力水平下Q235碳钢在5%NaCl盐雾中的腐蚀动力学拟合结果

图3 不同弹性拉应力水平下Q235碳钢在5%NaCl盐雾中暴露不同时间后的表面宏观形貌

图4 不同弹性拉应力水平下Q235碳钢在5%NaCl盐雾中暴露15 d后的锈层截面形貌和元素分布(a) 0σs (b) 0.5σs (c) 0.8σs (d) 0.95σs

图5 Q235碳钢在5%NaCl盐雾中暴露15 d后锈层的厚度随钢基体所受弹性拉应力水平的变化

图6 不同弹性拉应力水平下Q235碳钢在5%NaCl盐雾中暴露15 d后锈层的XRD谱和物相组成

图7 Q235碳钢在5%NaCl盐雾中暴露15 d后锈层的单位面积质量和密度随钢基体所受弹性拉应力水平的变化

图8 加载方式A和B下Q235碳钢在5%NaCl盐雾中暴露15 d后测得的开路电位随钢基体所受弹性拉应力水平的变化

图9 不同弹性拉应力水平的加载方式A和B下Q235碳钢在5%NaCl盐雾中暴露15 d后的EIS

表2 不同弹性拉应力水平的加载方式A和B下Q235碳钢在5%NaCl盐雾中暴露15 d后EIS的拟合结果

图10 Q235碳钢在5%NaCl盐雾中暴露15 d后锈层界面的等效电路图

图11 加载方式A和B下等效电路中电荷转移电阻(Rct)、锈层电阻(Rrust)与电容弥散系数(nrust)、扩散阻抗(W)随弹性拉应力水平的变化趋势

图12 锈层中r2 / r1、(r2 + r3) / r1和锈层密度随钢基体所受弹性拉应力水平的变化

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