金属腐蚀引发的经济损失与安全隐患已成为全球性重大挑战。环氧涂层虽应用广泛,但因其固化缺陷及亲水特性,易受腐蚀介质侵蚀,且损伤后难以自愈。微纳米容器作为智能填料,通过负载并响应性地释放缓蚀剂或修复剂,为实现环氧涂层的主动防护与自修复提供了有效途径。本文系统综述近年来微纳米容器在环氧防腐涂层领域的研究进展。首先,阐明无机、有机及复合微纳米容器的类型、结构特征与主要制备方法（如溶胶-凝胶法、原位聚合法、水热法、球磨法等）,并从化学键（共价键、配位键、离子键等）层面揭示了其结构-性能关系。其次,重点分析提升容器与环氧基体相容性的调控策略,涵盖偶联剂改性、聚合物包覆、生物基分子修饰、共价接枝、物理结构调控及基体改性,并指出界面黏附功的增加是相容性改善的关键标志。进而,深入探讨了微纳米容器提升涂层耐腐蚀性能的核心机制,包括力学性能增强（填充致密化、裂纹偏转、能量吸收）、物理屏障强化（填充、迷宫、屏障网络及疏水效应）、多重刺激响应（如pH、离子交换、氧化还原、机械损伤等）释放及其引发的化学修复（形成钝化/络合膜）与物理修复（裂纹填充固化）,强调了多机制在时空尺度上的协同防护效应。最后,指出了当前研究在相容性的理性设计、多机制时序匹配、长效服役工况验证及绿色智能化集成等方面面临的挑战,并展望未来发展方向,旨在为高性能智能防腐涂层的开发提供理论参考与技术支撑。
Abstract
The economic losses and safety hazards caused by metal corrosion have become a significant global challenge. Although epoxy coatings are widely used, their inherent curing defects and hydrophilic nature make them susceptible to attack by corrosive media, and they are difficult to self-heal after damage. Micro/nano containers, as intelligent fillers, offer an effective pathway to achieve active protection and self-healing for epoxy coatings by loading and responsively releasing corrosion inhibitors or healing agents. The work aims to systematically review the recent research progress of micro/nano containers in the field of epoxy anticorrosive coatings. Firstly, from the perspective of material systems and their preparation, the types, structural characteristics, and main fabrication methods of inorganic, organic, and composite micro/nano containers are elucidated. Inorganic containers mostly rely on sol-gel methods (hydrolysis-condensation forming covalent bond networks), hydrothermal/solvothermal methods (coordination bond self-assembly), physical/chemical precipitation methods (ionic bond nucleation), and ball milling (mechanically induced physical bonding) to construct rigid frameworks, possessing high strength and ordered channels. Organic containers form flexible polymer shells through in-situ polymerization (covalent crosslinking at oil-water interfaces), interfacial polymerization (oriented addition polymerization), or solvent evaporation (non-covalent physical deposition), endowing the coating with favorable tailorability and self-healing triggering capability. Composite containers couple the strong chemical bonds of the inorganic phase with the non-covalent/coordination bonds of the organic phase, achieving a synergistic multi-bond combination that integrates rigidity and flexibility. In particular, the introduction of emerging systems such as metal-organic frameworks and layered double hydroxides has expanded the functional designability from a single "encapsulation-release" mode to richer implementation forms, including "structural degradation enabling functional release" and "ion exchange as a response trigger". Secondly, to address the agglomeration and polarity mismatch with the epoxy matrix caused by surface hydroxyl groups of inorganic containers, strategies for improving compatibility are emphatically analyzed. These strategies encompass covalent bridging by coupling agents, polymer encapsulation, bio-based molecular modification, covalent grafting/non-covalent doping of organic molecules, physical structure regulation (particle size optimization, point-plane structures, hollow rough surfaces), and epoxy matrix modification (crosslinking network regulation, amphiphilic blending). The essence of all strategies lies in eliminating active surface hydroxyl groups, shielding interparticle forces, and increasing interfacial adhesion work. A multiscale characterization system based on "chemical bonds (FTIR/XPS)-dispersion morphology (SEM/TEM/DLS)-interfacial energy (contact angle/DMA)" must be established to systematically evaluate the compatibility improvement. Furthermore, the core mechanisms by which micro/nano containers enhance the corrosion resistance of coatings are thoroughly discussed. This mechanism has evolved into a three-level synergistic system: mechanical property enhancement-physical barrier reinforcement-responsive release and self-healing. Mechanical enhancement maintains structural integrity through densification filling, crack deflection, and energy absorption. Physical barrier reinforcement utilizes filling effects, labyrinth effects, barrier networks, and hydrophobic effects, following Fick's law to retard the permeation of corrosive media. Multiple stimuli responsiveness (e.g., pH, ion exchange, redox, mechanical damage) triggers the release, initiating chemical healing by forming passivation/complexation films and physical healing by crack filling and solidification, thereby achieving active intervention at the early stage of corrosion. Multi-stimuli responsive containers further enhance protection under complex service conditions through "orthogonality" and "temporal matching" designs. Research requires multiscale experimental characterization ranging from macroscopic electrochemical impedance spectroscopy, polarization curves, and salt spray tests to microscopic SEM/EDS, XPS, and scanning vibrating electrode techniques to provide a complete chain of evidence for each protection level. Finally, current challenges are identified, and future directions are prospected. Regarding compatibility, systematic studies should be conducted on the correlations between parameters such as surface chemistry, geometric structure, and surface energy of containers and the curing behavior and interfacial bonding strength of epoxy, to establish predictive models based on interfacial thermodynamics and kinetics. For multi-mechanism synergy, based on the spatiotemporal evolution characteristics of corrosion electrochemistry (initiation, development, propagation), hierarchical response systems should be designed to precisely connect barrier enhancement, inhibitor release, and self-healing, and their activation thresholds, action duration, and synergistic windows should be revealed. In terms of long-term service evaluation, multi-factor coupled service performance assessment methods need to be constructed, and correlation models between laboratory accelerated tests and actual engineering service life should be established. For greenization and intelligence, efforts should be made to promote environmentally friendly technologies such as bio-based materials, aqueous-phase synthesis, and low-temperature preparation, explore the transition from single-stimulus response to multi-stimulus synergistic response and from passive release to active sensing and feedback regulation, and construct a "sensing-response-healing" closed loop, thereby providing theoretical references and technical support for the development of high-performance intelligent anticorrosive coatings.
关键词
环氧涂层 /
微纳米容器 /
相容性 /
响应释放 /
调控机制
Key words
epoxy coating /
micro/nano container /
compatibility /
responsive release /
regulatory mechanism
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基金
湛江市科技计划项目（2025B01049,2026B01095）; 广东省南海海洋牧场智能装备重点实验室资助课题（2023B1212030003）; 广东省珠江学者人才计划（2025）; 广东省科协青年科技人才培育计划（SKXRC2026530,SKXRC2026506）; 广西重点研发计划项目（GK AB23026069）
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