9%Cr合金钢在含Cl－环境中的初期腐蚀行为及局部腐蚀起源

doi:10.11900/0412.1961.2021.00597

金属学报

2023, Vol. 59

Issue (7): 926-938 DOI: 10.11900/0412.1961.2021.00597

研究论文

本期目录 | 过刊浏览

9%Cr合金钢在含Cl^－环境中的初期腐蚀行为及局部腐蚀起源

陈润农¹^,²^,³, 李昭东¹(

), 曹燕光¹^,⁴, 张启富², 李晓刚³

¹钢铁研究总院工程用钢研究所北京 100081
²钢铁研究总院先进金属材料涂镀国家工程实验室北京 100081
³北京科技大学新材料技术研究院北京 100083
⁴马鞍山钢铁股份有限公司马鞍山 243003

Initial Corrosion Behavior and Local Corrosion Origin of 9%Cr Alloy Steel in Cl^－Containing Environment

CHEN Runnong¹^,²^,³, LI Zhaodong¹(

), CAO Yanguang¹^,⁴, ZHANG Qifu², LI Xiaogang³

¹Department of Structural Steels, Central Iron and Steel Research Institute, Beijing 100081, China
²National Engineering Laboratory of Advanced Coating Technology for Metals, Central Iron and Steel Research Institute, Beijing 100081, China
³Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
⁴Maanshan Iron & Steel Co. Ltd., Maanshan 243003, China

引用本文:

陈润农, 李昭东, 曹燕光, 张启富, 李晓刚. 9%Cr合金钢在含Cl^－环境中的初期腐蚀行为及局部腐蚀起源[J]. 金属学报, 2023, 59(7): 926-938.
Runnong CHEN, Zhaodong LI, Yanguang CAO, Qifu ZHANG, Xiaogang LI. Initial Corrosion Behavior and Local Corrosion Origin of 9%Cr Alloy Steel in Cl^－Containing Environment[J]. Acta Metall Sin, 2023, 59(7): 926-938.

全文: PDF(5401 KB) HTML

摘要:

通过干湿循环测试、SEM、TEM、XRD和电化学方法研究了一种9%Cr合金钢在含Cl^-环境中的初期腐蚀行为，探讨了复合夹杂物(Mg, Si, Al)O-MnS和富Cr的M₂₃C₆对其局部腐蚀行为的影响。结果表明，合金钢初期耐蚀性能较09CuPCrNi提高了12倍以上，在360 h的干湿循环过程中发生局部腐蚀，锈层下的蚀坑深度符合Lognormal分布，蚀坑的最大深度(D_max)与平均深度(D_ave)随时间(t)变化规律分别符合幂函数D_max = 8.4844 × t^0.65717和D_ave = 7.3181 × t^0.53866。合金钢锈层的致密度和α / γ^* (α-FeOOH / (γ-FeOOH + Fe₃O₄ + β-FeOOH)含量比)随腐蚀时间延长均不断增加，但高Cr的添加推迟了腐蚀进程，使得锈层未完整覆盖表面，仅提供了有限的保护能力，因而根据幂函数拟合失重数据得到的指数大于1。复合夹杂物(Mg, Si, Al)O-MnS通过MnS或单一MgO区域的局部优先溶解导致亚稳态点蚀，但其在2%NaCl溶液中浸泡300 min并未诱发周围基体溶解，而富Cr的M₂₃C₆析出导致基体的Cr消耗是优先诱发局部腐蚀的主要原因。

关键词 ：含Cl^-环境, 局部腐蚀, 夹杂物, M₂₃C₆, 9%Cr合金钢

Abstract：

The South China Sea is a marine atmosphere environment with high humidity, high salt content, and strong radiation. Traditional weathering steel and 3Ni advanced weathering steel cannot meet the service requirements in the South China Sea environment, necessitating the development of steel with improved corrosion resistance. Alloy steels with Cr of 2.5%-10% (mass fraction) provide a marginal gain in corrosion performance at a low cost and have great potential for marine atmospheric application. A 9%Cr alloy steel was designed to obtain higher corrosion resistance, and the relevant results can offer a reference for developing novel corrosion-resistant steels for the marine atmospheric environment. The initial corrosion behavior of 9%Cr alloy steel in a Cl^- containing environment was investigated using dry-wet cycle test, SEM, TEM, XRD, and electrochemical approaches, and the effects of composite inclusions (Mg, Si, Al)O-MnS and Cr-rich M₂₃C₆ on its local corrosion behavior were discussed. The findings demonstrate that the initial corrosion resistance of alloy steel was more than 12 times that of 09CuPCrNi, and local corrosion occurred during the 360-h dry-wet cycle. Pits' depth below the rust layer followed the lognormal distribution, and the pits' maximum depth (D_max) and average depth (D_ave) with time (t) were in line with the power functions D_max = 8.4844 × t^0.65717 and D_ave = 7.3181 × t^0.53866, respectively. The rust layer's compactness and the α / γ^* ratio increased over time, but the addition of high Cr delayed the corrosion. Thus, the rust layer did not entirely cover the surface and only provided limited protection, and an exponent value obtained by fitting the weight loss according to the power function was greater than 1. (Mg, Si, Al)O-MnS caused metastable pitting corrosion through a preferential dissolution of MnS or MgO regions, but its immersion in 2%NaCl solution for 300 min did not induce surrounding matrix's dissolution. The Cr consumption caused by Cr-rich M₂₃C₆'s precipitation was the primary reason for preferentially inducing local corrosion.

Key words： Cl^- containing environment local corrosion inclusion M₂₃C₆ 9%Cr alloy steel

收稿日期: 2021-12-31

ZTFLH:

TG174.22

基金资助:国家重点研发计划项目(2021YFB3701702);钢铁研究总院基金项目(20G61860A)

通讯作者: 李昭东，cisri_lizhaodong@126.com，主要从事高性能交通与建筑用钢的基础理论研究与关键技术开发

Corresponding author: LI Zhaodong, professor senior engineer, Tel: (010)62181284, E-mail: cisri_lizhaodong@126.com

作者简介: 陈润农，男，1993年生，博士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2021.00597 或 https://www.ams.org.cn/CN/Y2023/V59/I7/926

图1 9Cr钢的制造工艺示意图

表1 9Cr和09CuPCrNi钢的化学成分 (mass fraction / %)

图2 9Cr和09CuPCrNi钢的腐蚀速率和失重随时间的变化趋势

图3 9Cr钢腐蚀不同时间后的表面宏观和微观腐蚀形貌

表2 图3c1~c4中方形区域对应的EDS结果 (mass fraction / %)

图4 9Cr钢腐蚀不同时间后的锈层截面形貌和相应的主要元素分布

图5 9Cr钢腐蚀360 h后锈层截面的EPMA面扫描图

图6 9Cr钢腐蚀样品在2%NaCl溶液中的EIS及拟合等效电路图

表3 9Cr钢腐蚀样品在2%NaCl溶液中的EIS拟合数据

图7 9Cr钢腐蚀不同时间后表面腐蚀产物的XRD谱和半定量结果

图8 9Cr钢腐蚀不同时间后的表面蚀坑深度分布图和蚀坑深度变化规律

图9 9Cr钢腐蚀不同时间后表面蚀坑的径深比分布图

图10 9Cr钢在2%NaCl溶液中的极化曲线

图11 9Cr钢表面代表性亚稳态点蚀形貌

图12 2种典型复合夹杂物的形貌及EDS元素分布图

图13 2种典型复合夹杂物在2%NaCl溶液中浸泡不同时间后的腐蚀形貌

图14 9Cr钢在2%NaCl溶液中浸泡300 min后的典型局部腐蚀形貌及元素分布

图15 9Cr钢中M23C6的分布特征和成分分析

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