缺陷自预警涂层的触发机制及制备策略研究进展

doi:10.11902/1005.4537.2023.246

中国腐蚀与防护学报

2024, Vol. 44

Issue (3): 540-552 CSTR: 32134.14.1005.4537.2023.246 DOI: 10.11902/1005.4537.2023.246

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缺陷自预警涂层的触发机制及制备策略研究进展

李刚卿¹, 刘茜², 孙晓光¹, 潘景龙², 曹祥康², 董泽华²(

)

1.中车青岛四方机车车辆股份有限公司技术工程部青岛 266111
2.华中科技大学化学与化工学院材料化学与服役失效湖北省重点实验室武汉 430074

Research Progress on Trigger Mechanism and Preparation Strategy of Coatings of Defect Self-disclosure

LI Gangqing¹, LIU Xi², SUN Xiaoguang¹, PAN Jinglong², CAO Xiangkang², DONG Zehua²(

)

1. CRRC Qingdao Sifang Co., Ltd., Qingdao 266111, China
2. Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

引用本文:

李刚卿, 刘茜, 孙晓光, 潘景龙, 曹祥康, 董泽华. 缺陷自预警涂层的触发机制及制备策略研究进展[J]. 中国腐蚀与防护学报, 2024, 44(3): 540-552.
Gangqing LI, Xi LIU, Xiaoguang SUN, Jinglong PAN, Xiangkang CAO, Zehua DONG. Research Progress on Trigger Mechanism and Preparation Strategy of Coatings of Defect Self-disclosure[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(3): 540-552.

全文: PDF(11619 KB) HTML

摘要:

有机涂层防护是抑制海上平台、远洋货轮、油气管道、铁路设施等大型装备腐蚀的重要手段之一，然而在紫外、高低温或盐雾环境下有机涂层的老化降解在所难免。而如何及早发现涂层缺陷，实现装备装置涂层的预防性维修并确定其维修更换周期，对于提升防腐蚀成本效益比具有重要价值。基于此，针对涂层的老化缺陷实现早期发现和预警成为了新型功能涂层的研究热点之一。本文首先系统地总结了缺陷自预警涂层不同的触发机制，梳理了各类自预警涂层的传感机制、优缺点、影响荧光/颜色响应的因素；其次介绍了两种自预警涂层的制备策略，一是接枝指示基团修饰涂层制备新型本征自预警聚合物，二是使用纳米容器负载指示剂作为外援功能性填料，并对比分析两种策略的差异与局限性，重点阐明纳米负载容器在自预警涂层中起到的关键作用，以及不同类型自预警涂层与纳米容器的适配关系。最后本文还回顾了在自预警涂层基础上实现自预警自修复双功能涂层的研究进展，并展望了自预警涂层未来的发展前景，旨在为自预警涂层的设计与应用提供理论指导。

关键词 ：涂层老化, 自预警, 荧光探针, 颜色变化, 自修复

Abstract：

Organic coating is widely applied to hinder the corrosion of large-scale engineering facilities, such as offshore platforms, oceangoing freighters, oil and gas pipelines and rail equipment etc. However, coatings are often severely deteriorated in harsh service environments, thus leading to corrosion of metallic substrates, which may not only threaten the service safety of the engineering facilities but also cause significant economic losses. Moreover, the coating degradation is an unavoidable and spontaneous process, and it should be mentioned especially that some hidden coating defects are hard to be detected. Therefore, it has become a research hotspot to develop coatings with function of defect self-disclosure for early detection and maintenance of defects by applying color reaction or fluorescence probe technology. In this review, we summarize the latest advances in coatings of defect self-disclosure, as well as the relevant trigger mechanisms and preparation strategies. First, the coatings of defect self-disclosure can be classified as corrosion-triggered type and mechanical-triggered type based on their mechanisms. Then the corrosion-triggered coatings may be subdivided into pH response and metal ion response according to the fluorescence change or color reaction. Moreover, it sorts out the diverse characteristics of those coatings such as their sensing principles, influencing factors, advantages and drawbacks, and fluorescence/coloration performances. Second, two kinds of preparation strategies for coatings of defect self-disclosure are introduced, one is grafting indicator groups onto polymer chain segments to prepare coatings of intrinsic defect self-disclosure, and the other is to incorporate nano-containers loaded with indicator as the functional filler. The differences and limitations of these strategies are compared and analyzed, further focusing on the key role of nanocontainers and their compatibility with different types of coatings of defect self-disclosure. In addition, the corrosion inhibitors, healing agents, and polymer microcapsules in the coatings of defect self-disclosure can not only realize defect indication but also endow their corrosion self-healing performance for boosting their application in the industrial field. Finally, it is envisioned the development prospect of coatings of defect self-disclosure to provide theoretical guidance for the design and application of the coatings of defect self-disclosure.

Key words： coating aging self-reporting fluorescent probe color change self-healing

收稿日期: 2023-08-10 32134.14.1005.4537.2023.246

ZTFLH:

TG174.4

基金资助:国家重点研发计划(2020YFE0204900);中车重点科研项目(2021CDB292)

通讯作者: 董泽华，E-mail: zhdong@hust.edu.cn，研究方向为腐蚀与防护

Corresponding author: DONG Zehua, E-mail: zhdong@hust.edu.cn

作者简介: 李刚卿，男，1971年生，硕士，教授级高级工程师(共同一作)
刘茜，女，1999年生，硕士生(共同一作)

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图1 酚酞变色机理[17]

图2 荧光素[24]，FD1[26]和香豆素120[28]的荧光机理

图3 菲啰啉[34]和单宁酸[32]的络合机理

图4 DCF颜色变化原理，空白环氧涂层与含10%DCF胶囊涂层划痕预警对比，含15%DCF胶囊涂层对不同划痕深度的预警和机械损伤颜色变化示意图[43]

图5 螺吡喃修饰涂层变色机理[45]

图6 化学修饰丙烯酸涂层的合成以及含AMP 0%、2.5%和3%涂层在3.5%NaCl溶液浸泡前后对比[55]

图7 MSN-PC的制备以及空白环氧涂层与含4% MSN-PC环氧涂层的盐雾实验[69]

表1 部分自预警涂层颜色指示剂及其变化应用

图8 PDVB-graft-P(DVB-co-AA)合成以及包含空白涂层和智能涂层的铜合金和铝合金在3.5%NaCl溶液中浸泡6 h的表面[72]

图9 H2PNL20(含PNL)和H2PNL20MBT5 (含PNL + MBT )的涂层浸泡在3.5%NaCl 溶液中[74]

图10 CVL变色机理和WEP智能涂层原理图[71]

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