羟基亚乙基二膦酸对20SiMn钢在含Cl-混凝土模拟孔隙液中的缓蚀行为

doi:10.11900/0412.1961.2019.00382

金属学报

2020, Vol. 56

Issue (6): 898-908 DOI: 10.11900/0412.1961.2019.00382

本期目录 | 过刊浏览

羟基亚乙基二膦酸对20SiMn钢在含Cl^-混凝土模拟孔隙液中的缓蚀行为

曹凤婷¹^,², 魏洁¹, 董俊华¹(

), 柯伟¹, 王铁钢², 范其香²

^1.中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016
^2.天津职业技术师范大学机械工程学院天津市高速切削与精密加工重点实验室天津 300222

Corrosion Inhibition Behavior of 1-Hydroxyethylidene-1, 1-Diphosphonic Acid on 20SiMn Steel in Simulated Concrete Pore Solution Containing Cl^-

CAO Fengting¹^,², WEI Jie¹, DONG Junhua¹(

), KE Wei¹, WANG Tiegang², FAN Qixiang²

^1.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^2.Tianjin Key Laboratory of High Speed Cutting and Precision Machining, School of Mechanical Engineering, Tianjin University of Technology and Education, Tianjin 300222, China

引用本文:

曹凤婷, 魏洁, 董俊华, 柯伟, 王铁钢, 范其香. 羟基亚乙基二膦酸对20SiMn钢在含Cl^-混凝土模拟孔隙液中的缓蚀行为[J]. 金属学报, 2020, 56(6): 898-908.
Fengting CAO, Jie WEI, Junhua DONG, Wei KE, Tiegang WANG, Qixiang FAN. Corrosion Inhibition Behavior of 1-Hydroxyethylidene-1, 1-Diphosphonic Acid on 20SiMn Steel in Simulated Concrete Pore Solution Containing Cl^-[J]. Acta Metall Sin, 2020, 56(6): 898-908.

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摘要:

采用电化学技术(动电位极化曲线、自腐蚀电位、EIS以及Mott-Schottky曲线)和表面分析方法(SEM、XPS)研究了羟基亚乙基二膦酸(HEDP)对空冷20SiMn低合金钢在含Cl^-的高碱性混凝土模拟孔隙液中的缓蚀作用及机理。结果表明， HEDP对20SiMn钢在含1 mol/L NaCl饱和Ca(OH)₂溶液中的缓蚀效果随HEDP浓度的升高存在极值，最佳浓度为1.441×10^-4 mol/L。在此浓度下HEDP将20SiMn钢的钝性保持时间从6 h延长至9 h，缓蚀效率达到46.45%~59.78%。在发生点蚀的情况下，HEDP对点蚀的发展亦有显著的抑制作用，缓蚀效率超过93%。电化学和表面分析结果表明，HEDP优先吸附在钝化膜表面，通过竞争吸附机制屏蔽了侵蚀性Cl^-向钝化膜表面的附着，从而对其产生保护作用。

关键词 ：羟基亚乙基二膦酸, 腐蚀, 缓蚀剂, 吸附, 混凝土模拟孔隙液

Abstract：

The corrosion of steel rebar in concrete will be induced once the passive film is destroyed by chlorides or carbonation. Several techniques have been employed to reduce the corrosion so far. Among them, adding inhibitors is effective one because of its advantages, such as high efficiency and easy handling. 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), a typical organic phosphonic acid, is a low toxic corrosion inhibitor for steel and iron in neutral aerobic environment. This compound was first used as scale inhibitor in water treatment industry, such as cooling water circulation system. The molecule of HEDP has two phosphate groups, making it a powerful chelating ability with metallic ions. However, most of the current studies of HEDP focus on neutral or near-neutral systems, and there are few reports on the corrosion inhibition of steel reinforcement in alkaline environment. Therefore, it is not clear whether HEDP can play the role of corrosion inhibitor by protecting the passive film and resist foreign corrosive Cl^-. In this work, the inhibition effect of HEDP towards 20SiMn steel was investigated in simulated concrete pore solution contaminated by Cl^- (Sat.Ca(OH)₂+1 mol/L NaCl) by electrochemical methods (corrosion potential, potentiodynamic polarization curves, EIS and Mott-Schottcky curves) and surface analysis techniques (SEM, XPS). The results showed that HEDP was a mixed inhibitor and its inhibition efficiency increased first and then decreased with the increase of concentration, the optimal concentration is 1.441×10^-4 mol/L . At the optimal concentration, HEDP could obviously enlarge the passive region, prolong the passive period of 20SiMn steel from 6 h to 9 h , and improve the charge-transfer resistance significantly with the inhibition efficiency around 46.45%~59.78%. When pitting corrosion occurs, HEDP could hinder its development with the inhibition efficiency over 93%. The inhibition mechanism was the preferential adsorption of HEDP over Cl^- by forming a complete adsorption film outside the passive film of the steel.

Key words： HEDP corrosion corrosion inhibitor adsorption simulated concrete pore solution

收稿日期: 2019-11-11

ZTFLH:

TG174

基金资助:国家自然科学基金项目(U1867216);国家自然科学基金项目(51501201);国家自然科学基金项目(51801219)

作者简介: 曹凤婷，女，1988年生，讲师，博士

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https://www.ams.org.cn/CN/10.11900/0412.1961.2019.00382 或 https://www.ams.org.cn/CN/Y2020/V56/I6/898

图1 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2中添加不同浓度羟基亚乙基二磷酸(HEDP)时的动电位极化曲线

图2 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2中添加不同浓度HEDP时的EIS

图3 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2溶液中的EIS

图4 20SiMn钢在添加1.441×10-4 mol/L HEDP的1 mol/L NaCl饱和Ca(OH)2溶液中的EIS

图5 钝化阶段、点蚀阶段无感抗弧以及点蚀阶段有感抗弧的等效模拟电路图

表1 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白及添加1.441×10-4 mol/L HEDP溶液中EIS的拟合结果

图6 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白和添加1.441×10-4 mol/L HEDP溶液中膜层电阻(Rf)、电荷转移电阻(Rct)随浸泡时间的变化

图7 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白和添加1.441×10-4 mol/L HEDP溶液中的自腐蚀电位

图 8 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白和添加1.441×10-4 mol/L HEDP溶液中浸泡7 h除锈的SEM像

图9 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白和添加1.441×10-4 mol/L HEDP溶液中的Mott-Schottky 曲线

图10 20SiMn钢在1 mol/L NaCl饱和Ca(OH)2空白或添加1.441×10-4 mol/L HEDP溶液中浸泡1 h的XPS分峰处理结果

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