ZnAlCe-NO2 水滑石@硅烷涂层的氯离子捕获和响应缓蚀行为

doi:10.11902/1005.4537.2025.085

中国腐蚀与防护学报

2026, Vol. 46

Issue (1): 207-219 CSTR: 32134.14.1005.4537.2025.085 DOI: 10.11902/1005.4537.2025.085

研究报告

本期目录 | 过刊浏览

ZnAlCe-NO₂ 水滑石@硅烷涂层的氯离子捕获和响应缓蚀行为

谭敬莎, 郭艺超, 陈俊霖, 盖文峰, 孟国哲(

)

中山大学化学工程与技术学院珠海 519082

Chloride Ion Capture and Responsive Corrosion Inhibition Behavior of ZnAlCe-NO₂ Hydrotalcite @ Silane Coating

TAN Jingsha, GUO Yichao, CHEN Junlin, GAI Wenfeng, MENG Guozhe(

)

School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, China

引用本文:

谭敬莎, 郭艺超, 陈俊霖, 盖文峰, 孟国哲. ZnAlCe-NO₂ 水滑石@硅烷涂层的氯离子捕获和响应缓蚀行为[J]. 中国腐蚀与防护学报, 2026, 46(1): 207-219.
Jingsha TAN, Yichao GUO, Junlin CHEN, Wenfeng GAI, Guozhe MENG. Chloride Ion Capture and Responsive Corrosion Inhibition Behavior of ZnAlCe-NO₂ Hydrotalcite @ Silane Coating[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(1): 207-219.

全文: PDF(12798 KB) HTML

摘要:

水滑石(LDH)独特的阳离子和阴离子层状结构，赋予层间阴离子易于和环境离子交换的特性，从而使其成为一种优异的无机纳米容器。本研究利用一步共沉淀法制备装载NO $2 -$ 缓蚀剂的ZnAlCe-NO₂ LDH，将其添加到溶胶凝胶硅烷涂层中。涂层服役过程中，除了缺陷处局部水解酸化环境中LDH主板层Ce³⁺响应释放，对基体金属起到缓蚀作用外，处于高能状态ZnAlCe-NO₂LDH层间的NO $2 -$ 与渗入涂层中的Cl^-亦会自发发生交换响应，不仅将游离的Cl^-捕获固定在LDH结构内，同时还会释放层间预先负载的缓蚀剂，增强涂层的防护性能，从而起到“一石二鸟”的作用。在0.05 mol/L NaCl溶液中的电化学测试表明，ZnAlCe-NO₂ LDH对碳钢缓蚀效率可达97.57%；与空白溶胶凝胶涂层相比，掺杂2.5 mg/mL ZnAlCe-NO₂ LDH的溶胶凝胶涂层的腐蚀防护性能得到了显著提升。

关键词 ：水滑石, 离子交换作用, 缓蚀剂控释, 溶胶凝胶涂层, 自修复

Abstract：

The unique lamellar structure of cations and anions in hydrotalcite (LDH) endows the interlayer anions with the characteristic of easy ion exchange with the environment, making it an excellent inorganic nanocontainer. In this study, a corrosion inhibitor ZnAlCe-NO₂ LDH loaded with NO $2 -$ was prepared by one-step co-precipitation method and which then was added to the sol gel silane coating. It may be reasonably inferred that at defect sites of the coating Ce ions within the LDH lamellae may be response and release where local hydrolysis acidification environment has been generated during the coating service, which then act as a means to inhibit the corrosion of the substrate metal; Meanwhile, the NO $2 -$ of high energy state situated between the ZnAlCe-NO₂ LDH lamellae and will spontaneously exchange-react with the infiltrated chloride ions (Cl^-) in the coating, which result in not only capturing and fixing the free Cl^- in the LDH lamellar structure, but also releasing the pre-loaded corrosion inhibitor within the LDH lamellae so that to enhance the protective performance of the coating, just like a Chinese proverb “kill two birds with one stone”. Electrochemical tests in a 0.05 mol/L NaCl solution showed that ZnAlCe-NO₂ LDH had a corrosion inhibition efficiency of 97.57% for carbon steel. Compared with the blank sol gel coating, the corrosion protection performance of the sol gel coating doped with 2.5 mg/mL ZnAlCe-NO₂ LDH has been significantly improved.

Key words： hydrotalcite ion exchange corrosion inhibitor controlled release sol gel coating self repair

收稿日期: 2025-03-12 32134.14.1005.4537.2025.085

ZTFLH:

TG174

基金资助:国家自然科学(52171093);国家重点研发计划(2019YFE0111000)

通讯作者: 孟国哲，E-mail：menggzh3@mail.sysu.edu.cn，研究方向为材料腐蚀与防护

作者简介: 谭敬莎，女，1999年生，硕士生

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.085 或 https://www.jcscp.org/CN/Y2026/V46/I1/207

图1 水滑石及掺杂LDH-NO2-的硅烷溶液溶胶凝胶涂层的制备示意图

图2 ZnAl-LDH和ZnAlCe-NO2 LDH的SEM图、ZnAlCe-NO2 LDH的EDS能谱图，不同水滑石样品的XPS谱图及XRD图，FT-IR图，TG和DTG图以及不同NaCl浓度下，Q235碳钢在空白溶液和添加ZnAlCe-NO2 LDH溶液中的腐蚀电位和低频模值的变化图，ZnAlCe-NO2 LDH水滑石样品的氯离子吸附、缓蚀剂释放曲线

图3 碳钢在添加ZnAlCe-NO2 LDH溶液中的Bode和Nyquist图。碳钢在NaCl (0.05 mol/L)溶液与添加ZnAlCe-NO2 LDH的NaCl (0.05 mol/L)混合溶液中浸泡不同时间后的极化曲线图及EIS拟合的等效电路模型

表1 Q235碳钢在NaCl混合溶液中浸泡不同时间的EIS拟合参数

图4 碳钢分别在0.05 mol/L NaCl溶液、S/LDH-NO2溶液中浸泡24 h后的显微形貌；碳钢分别在0.05 mol/L NaCl空白溶液和S/LDH-NO2溶液中浸泡24 h后的FT-IR图和XRD图谱及ZnAlCe-NO2 LDH样品在NaCl溶液中离子交换前后的XRD图谱

图5 空白溶胶凝胶涂层、ZnAlCe-NO2 LDH掺杂的溶胶凝胶涂层的表面SEM图谱、空白溶胶凝胶涂层截面及能谱图及ZnAlCe-NO2 LDH掺杂的溶胶凝胶涂层截面及能谱图

图6 在0.05 mol/L NaCl溶液中浸泡不同时间后的不同的涂层的Bode图和Nyquist图模型a及等效电路(R(Q(R(QR))))

图7 EIS拟合得到的Rc、Qc、Rct随浸泡时间的变化曲线和低频模值的变化曲线，开路变化曲线及不同涂层样品在NaCl溶液中浸泡6 h后的极化曲线图

图8 空白硅烷涂层(SC)和溶胶凝胶涂层(SC/NO2-LDH2.5)在NaCl溶液中浸泡30 min和90 min后测得的SKP图

图9 掺杂溶胶凝胶涂层的腐蚀防护机理

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