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金属学报  2024, Vol. 60 Issue (1): 43-56    DOI: 10.11900/0412.1961.2022.00007
  研究论文 本期目录 | 过刊浏览 |
Cu含量对管线钢耐微生物腐蚀性能的影响
曾云鹏1,2, 严伟2,3(), 史显波2,3, 闫茂成2, 单以银2,3, 杨柯2
1 中国科学技术大学 材料科学与工程学院 沈阳 110016
2 中国科学院金属研究所 师昌绪先进材料创新中心 沈阳 110016
3 中国科学院金属研究所 中国科学院核用材料与安全评价重点实验室 沈阳 110016
Effect of Copper Content on the MIC Resistance in Pipeline Steel
ZENG Yunpeng1,2, YAN Wei2,3(), SHI Xianbo2,3, YAN Maocheng2, SHAN Yiyin2,3, YANG Ke2
1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
3 CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
引用本文:

曾云鹏, 严伟, 史显波, 闫茂成, 单以银, 杨柯. Cu含量对管线钢耐微生物腐蚀性能的影响[J]. 金属学报, 2024, 60(1): 43-56.
Yunpeng ZENG, Wei YAN, Xianbo SHI, Maocheng YAN, Yiyin SHAN, Ke YANG. Effect of Copper Content on the MIC Resistance in Pipeline Steel[J]. Acta Metall Sin, 2024, 60(1): 43-56.

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摘要: 

含Cu耐微生物腐蚀管线钢的开发和应用是解决管道微生物腐蚀难题的有效措施。本工作利用电化学测试及SEM、激光共聚焦显微镜(CLSM)等分析技术，研究了不同Cu含量(0、0.7%、1.34%，质量分数)的X65级管线钢在无菌和接种硫酸盐还原菌(SRB)的近中性模拟土壤浸出液(NS4)中的腐蚀行为，为耐微生物腐蚀管线钢的优化设计提供依据。结果表明，随着Cu含量的升高，含Cu管线钢的抗菌性能和耐蚀性能均有所提高；当Cu含量从0增加到0.70%时，试样表面的点蚀坑密度从714 cm-2下降到244 cm-2；当Cu含量达到1.34%时，点蚀坑密度进一步下降到67 cm-2；含Cu钢在腐蚀过程中持续释放的铜离子在接菌环境中的杀菌作用和其对腐蚀产物层的改善作用，以及其在无菌环境中所形成的Cu2O等保护性腐蚀产物是含Cu管线钢具有优异耐蚀性能的关键原因。
关键词 ： 微生物腐蚀,  硫酸盐还原菌,  含Cu管线钢,  抗菌性能,  耐蚀性能    
Abstract：

Microbiologically induced corrosion (MIC), particularly those caused by sulfate-reducing bacteria (SRB), is considered as a destructive mechanism in buried pipeline steels, which has received considerable attention since its discovery a century ago. Research has shown that sessile cells that are attached to a metal surface embedded in biofilms with extracellular polymeric substances (EPS) are responsible for the occurrence of MIC. However, the commonly used MIC control strategy, i.e., biocides, cannot perform sterilization of sessile cells because of the protection of the biofilm. Cu-bearing pipeline steel is a newly developed steel that can be used for MIC control in buried pipes. The continuous release of cytotoxic Cu ions from the steel matrix leads to MIC resistance. However, the influence of Cu content on MIC resistance remains unclear. A lower Cu content in steel is not beneficial to its MIC resistance, whereas a higher Cu content can increase the cost and may cause “hot shortness” during thermal processing. Therefore, clarifying the influence of Cu content on the properties of Cu-bearing pipeline steel is important for the practical application of the steel. In the present study, the influence of Cu content (0, 0.7%, and 1.34%; mass fraction) on the corrosion behavior of X65 grade Cu-bearing pipeline steel was investigated through electrochemical measurements and surface analysis during 14 d immersion in sterile and SRB-inoculated NS4 solutions, respectively. Experimental results demonstrated that the antibacterial properties and corrosion resistance of the steel improved with the increase of Cu content. When Cu content was increased to 1.34%, the pitting corrosion of the steel in the SRB-inoculated medium was almost suppressed. The protective corrosion products formed in the sterile medium and antibacterial Cu ions continuously released from the steel in the SRB-inoculated medium resulted in the remarkable corrosion resistance of Cu-bearing pipeline steels.
Key words： microbiologically induced corrosion    sulfate reduced bacteria (SRB)    Cu-bearing pipeline steel    antibacterial property    corrosion resistance
收稿日期: 2022-01-06     
ZTFLH:  TG174.2  
基金资助:国家自然科学基金项目(U1906226)
通讯作者: 严 伟，weiyan@ima.ac.cn，主要从事先进钢铁结构材料设计与组织性能控制方面的研究
Corresponding author: YAN Wei, professor, Tel: (024)83978990, E-mail: weiyan@ima.ac.cn
作者简介: 曾云鹏，男，1992年生，博士生
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https://www.ams.org.cn/CN/10.11900/0412.1961.2022.00007      或      https://www.ams.org.cn/CN/Y2024/V60/I1/43

SteelCSiMnCuNbTiMoFe
1#0.020.010.071.340.040.0170.1Bal.
2#0.020.010.050.700.040.0170.1Bal.
3#0.020.010.05－0.040.0170.1Bal.
表1  实验用钢的成分 (mass fraction / %)
图1  不同Cu含量管线钢的显微组织
图2  灭菌和接菌NS4溶液中不同Cu含量管线钢的开路电位随时间的变化
图3  不同Cu含量管线钢在灭菌和接菌NS4溶液的线性极化电阻(Rp)随时间的变化
图4  不同Cu含量管线钢在无菌和接菌NS4溶液中浸泡14 d后的动电位极化曲线
图5  不同Cu含量管线钢在无菌和接菌NS4溶液中的Nyquist谱随时间的变化
图6  用于EIS拟合的等效电路模型
SteelTime / dRs / (Ω·cm2)QdlRct / (Ω·cm2)χ2
Ydl / (S·s n ·cm-2)ndl
NS-1#1193.61.387 × 10-40.83651.733 × 1046.07 × 10-4
2188.87.166 × 10-50.89531.881 × 1058.79 × 10-4
4175.85.981 × 10-50.90824.377 × 1057.93 × 10-4
7169.25.488 × 10-50.91105.946 × 1058.95 × 10-4
14141.95.519 × 10-50.91046.011 × 1059.05 × 10-4
NS-2#1198.81.427 × 10-40.83856.071 × 1048.29 × 10-4
2196.15.011 × 10-50.89159.385 × 1041.05 × 10-3
4183.63.830 × 10-50.93853.809 × 1059.87 × 10-3
7171.43.783 × 10-40.94255.215 × 1051.01 × 10-3
14148.44.342 × 10-30.94784.932 × 1059.08 × 10-4
NS-3#1193.48.350 × 10-50.84611.814 × 1046.85 × 10-4
2190.14.959 × 10-50.91821.428 × 1051.15 × 10-3
4179.44.756 × 10-50.93691.956 × 1059.09 × 10-4
7166.55.263 × 10-50.94132.121 × 1055.82 × 10-4
14143.97.236 × 10-50.94431.481 × 1056.28 × 10-4
表2  灭菌NS4溶液中的EIS拟合结果
图7  不同Cu含量管线钢在灭菌和接菌NS4溶液中Rct及(Rct+Rf)随时间的变化
图8  不同Cu含量管线钢在接菌NS4溶液中浸泡14 d后的CLSM像
Steel

Time

d

Rs

Ω·cm2

Qf

Rf

Ω·cm2

Qdl

Rct

Ω·cm2

χ2
Yf / S·s n ·cm-2nfYdl / (S·s n ·cm-2)ndl
SRB-1#1216.45.25 × 10-30.91026.627 × 1044.71 × 10-4
2201.88.80 × 10-40.91005.509 × 1048.09 × 10-4
4180.27.73 × 10-30.471347.93.05 × 10-30.95863.897 × 1043.79 × 10-4
7172.51.07 × 10-20.428046.54.51 × 10-30.95821.451 × 1052.43 × 10-5
14153.07.92 × 10-50.468325.52.38 × 10-30.95994.578 × 1059.57 × 10-4
SRB-2#1223.65.50 × 10-40.91345.686 × 1045.74 × 10-4
2205.96.30 × 10-40.91075.136 × 1041.34 × 10-3
4184.05.25 × 10-30.517162.06.83 × 10-50.86133.695 × 1047.08 × 10-4
7166.19.96 × 10-30.487164.34.91 × 10-30.96797.404 × 1041.95 × 10-5
14150.59.37 × 10-20.432668.42.88 × 10-30.93833.659 × 1056.33 × 10-4
SRB-3#1336.71.202 × 10-40.80965.097 × 1045.74 × 10-4
2311.77.821 × 10-50.87634.003 × 1041.34 × 10-3
4184.35.62 × 10-30.538546.83.358 × 10-30.96543.486 × 1043.32 × 10-5
7169.98.93 × 10-30.441157.35.402 × 10-30.96584.555 × 1041.35 × 10-5
14154.87.00 × 10-50.441763.04.840 × 10-30.95991.068 × 1051.07 × 10-3
表3  接菌NS4溶液中的EIS拟合结果
图9  不同Cu含量管线钢在灭菌和接菌NS4溶液中浸泡14 d后的表面腐蚀产物形貌SEM像
图10  不同Cu含量管线钢在无菌和接菌NS4溶液中浸泡14 d后表面腐蚀产物的XPS全谱和EDS分析结果
图11  不同Cu含量管线钢在无菌和接菌NS4溶液中浸泡14 d后表面腐蚀产物中Cu的精细谱
图12  不同Cu含量管线钢在无菌和接菌NS4溶液中浸泡14 d后去除腐蚀产物后的表面形貌
图13  不同Cu含量管线钢在接菌NS4溶液中浸泡14 d后的表面点蚀坑统计结果
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