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pH 响应型中空介孔有机硅纳米容器及其环氧复合防腐涂层的研究

  • 李 薛 ,
  • 孙振华 ,
  • 杨 珂 ,
  • 李俊仪 ,
  • 张世龙 ,
  • 艾彩娇 ,
  • 李春玲
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  • 1. 中国石油化工股份有限公司胜利油田分公司技术检测中心,山东东营257000;

    2. 中石化安全工程研究院有限公司,山东青岛266000;

    3. 胜利油田检测评价研究有限公司,山东东营257000;

    4. 中国石油大学(华东)材料科学与工程学院,山东青岛266580

网络出版日期: 2026-03-09

基金资助

中国石油化工股份有限公司科技项目:滩海环境下储罐防腐隔热材料研发及应用研究(224130)

Research on pH-responsive Hollow Mesoporous Organosilica Nanocapsules and Their Composite Anticorrosive Coating

  • LI Xue ,
  • SUN Zhenhua ,
  • YANG Ke ,
  • LI Junyi ,
  • ZHANG Shilong ,
  • AI Caijiao ,
  • LI Chunling
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  • 1. Technical Testing Center of Shengli Oilfield Branch of China Petrochemical Corporation,Dongying,Shandong 257000,China;

    2. Sinopec Safety Engineering Research Institute Co., Ltd., Qingdao,Shandong 266000,China;

    3. Shengli Oilfield Testing and Evaluation Research Co., Ltd., Dongying,Shandong 257000,China;

    4. College of Materials Science and Engineering,China University of Petroleum(East China),Qingdao,Shandong 266580,China

Online published: 2026-03-09

摘要

【目的】针对传统防腐涂层中缓蚀剂直接掺杂易引发提前释放、涂层结构破坏及防护效果衰减等问题,构建一种基于 pH响应型智能纳米容器的自修复环氧复合涂层体系。【方法】通过硬模板法设计合成具有中空介孔结构的有机硅纳米容器( HPMO),结合真空浸渍技术负载缓蚀剂 2-巯基苯并噻唑( MBT),构建 HPMO@MBT智能防腐体系,通过调控 HPMO@MBT添加量制备环氧树脂复合涂层,并系统考察了纳米容器结构特征、缓蚀剂释放行为及复合涂层的防腐性能。【结果】 HPMO具备高比表面积和均匀介孔分布, MBT负载量达 17. 5%,且在酸性环境中可快速响应释放。电化学阻抗谱( EIS)及划痕试验证实,当 HPMO@MBT质量分数为 1%时,复合涂层在 3. 5%NaCl溶液中浸泡 15 d过程中低频阻抗衰减速率明显减缓,并在一定时间尺度内呈现出由下降向回升或稳定转变的演化特征,反映了涂层屏障作用与界面抑制效应的协同贡献。划痕浸泡试验结果显示,损伤区域检测到 N、S元素的富集分布,指示缓蚀剂在腐蚀诱导条件下发生定向迁移并参与界面保护过程。过量添加 HPMO@MBT(>1%)则可能因纳米容器聚集及局部孔隙率升高而削弱涂层防护性能。【结论】通过合理设计纳米容器结构与 HPMO@MBT添加量,可在保证涂层结构完整性的前提下实现缓蚀剂的稳定储存与环境响应释放,从而提升涂层在局部损伤条件下的防腐稳定性。

本文引用格式

李 薛 , 孙振华 , 杨 珂 , 李俊仪 , 张世龙 , 艾彩娇 , 李春玲 . pH 响应型中空介孔有机硅纳米容器及其环氧复合防腐涂层的研究[J]. 涂料工业, 2026 , 56(3) : 9 -17 . DOI: 10.12020/j.issn.0253-4312.2025-145

Abstract

[Objective]As the traditional anti-corrosion coating which direct doping of corrosioninhibitor is easy to trigger the problems of early release,coating structure damage and attenuation of protective effect,this paper constructs a self-repairing epoxy composite coating system based on pH responsive intelligent nanocontainers.[Methods] Silicone nanocontainers(HPMO) with hollow mesoporous structure were designed and synthesised by the hard template method,combined with vacuum impregnation technique to load the corrosion inhibitor 2-mercaptobenzothiazole(MBT), the smart anticorrosion system of HPMO@MBT was then constructed. The epoxy composite coatings wereprepared by regulating the addition amount of HPMO@MBT nanocontainers. The structural characteristics of the nanocontainer,the release behaviour of the corrosion inhibitor and the anticorrosion performance of composite coating were systematically investigated.[Results]The results showed that HPMO possessed a high specific surface area and uniform mesoporous distribution,and the MBT loading reached 17. 5%,which could be released quickly in response to the acidic environment.Electrochemical impedance spectroscopy(EIS)and scratch tests revealed that the composite coatingexhibited a significantly slowed low-frequency impedance decay rate during 15 days of immersion in a
3. 5%NaCl solution,when HPMO@MBT mass fraction is 1%. Over a specific time scale,it demonstrated an evolutionary shift from decline to recovery or stabilization,reflecting the synergisticcontribution of the coating's barrier function and interfacial inhibition effect. Scratch immersion resultsrevealed enriched distributions of N and S elements within the damaged area,indicating directed migration of the corrosion inhibitor under corrosion-induced conditions and its participation in interfacial protection. Excessive HPMO@MBT addition(>1%)may weaken coating performance due to nanocontainer aggregation and increased local porosity.[Conclusion]The above results indicate that by reasonably designing the structure of the nanocontainer and the HPMO@MBT addition amount,the stable storage and environmentally responsive release of corrosion inhibitors can be achieved under thepremise of ensuring the structural integrity of the coating,the anti-corrosion stability of the coating under the condition of local damage is enhanced.
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