金属有机框架材料在防腐涂层中的应用进展*

孔文泉; 魏凯; 袁钰婕; 刘文会; 张优

引用本文:	孔文泉,魏凯,袁钰婕,刘文会,张优.金属有机框架材料在防腐涂层中的应用进展*[J].中国表面工程,2023,36(4):51~64
	KONG Wenquan,WEI Kai,YUAN Yujie,LIU Wenhui,ZHANG You.Research Progress of Metal-organic Frameworks in Anti-corrosion Coatings[J].China Surface Engineering,2023,36(4):51~64

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金属有机框架材料在防腐涂层中的应用进展*
孔文泉¹, 魏凯¹, 袁钰婕¹, 刘文会², 张优¹
1.北京石油化工学院新材料与化工学院北京 102617;2.国家管网集团科学技术研究总院廊坊 065000

摘要:

金属有机框架材料是由金属离子和有机配体自组装而成的多孔配位聚合物，具有大比表面积、结构功能可调、高孔隙率、高表面活性等优势，金属有机框架材料在金属防腐领域表现出巨大的应用潜力，然而还少有相关的研究综述，有必要对目前金属有机框架材料在金属表面防腐涂层领域的研究成果进行综述。系统总结近年来该领域的相关研究成果，以金属有机框架材料的自身特性和防腐机理为出发点，分类概述金属有机框架材料功能性填料在防腐涂层中的应用以及防腐转化膜材料的最新研究。相关研究结果表明：金属有机框架材料作防腐涂层的功能性填料或防腐转化膜能极大增强对金属的防腐保护，金属有机框架材料功能性填料可改善涂层的致密度与相容性，作为理想容器负载活性剂实现了涂层的自修复、腐蚀自预警等功能性；另外，直接在金属表面制备金属有机框架材料防腐转化膜实现了涂层的主动防护（物理阻隔效应）和被动防护（响应释放缓蚀剂），将金属有机框架材料应用在防腐涂层中增强了对金属的防护性能，延长了金属基体的使用寿命。讨论了金属有机框架材料在应用过程中存在的问题并提出可行的解决途径，对金属有机框架材料在金属防腐涂层领域的应用前景和发展方向进行展望。

关键词: 金属有机框架腐蚀防护防腐涂层填料转化膜

DOI：10.11933/j.issn.1007?9289.20220923002

分类号:TG178

基金项目:北京市自然科学基金资助项目（2182017，2202017）

Research Progress of Metal-organic Frameworks in Anti-corrosion Coatings

KONG Wenquan¹, WEI Kai¹, YUAN Yujie¹, LIU Wenhui², ZHANG You¹

1.College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology,Beijing 102617 , China;2.PipeChina North Pipeline Company-Science and Technology Institute, Langfang 065000 , China

Abstract:

Metallic corrosion has been a major challenge worldwide for a long time. In addition to significant economic losses, there are concomitant risks of security loss and environmental pollution. Coating can be an economic and effective method to retard the corrosion of metals. However, a simple passive anticorrosion coating is difficult to achieve a long-term and effective anticorrosion effect. Once the coating is damaged, it fails, and even a more serious local corrosion occurs. In recent years, an intelligent self-healing anticorrosion coating has been proposed based on micro- and nanocontainers that can release functional substances such as corrosion inhibitors according to environmental changes, independently repair the damaged parts of the coating, restore the protective ability of the coating, and prolong the service life of the metal matrix. The metal-organic framework material is a porous coordination polymer composed of metal ions and organic ligands, which has a large specific surface area, tunable structure and function, high porosity, high surface activity, etc. Recent studies have shown that metal-organic framework materials have high application potentials in the field of metal anticorrosion. The reviews on the related studies are still rather scarce. It is necessary to review the current research results of metal-organic framework materials in the field of anticorrosion coatings on metal surfaces. This paper systematically summarizes the related research results in this field. Based on the characteristics and anticorrosion mechanism of metal-organic framework materials, this paper summarizes the research progress of metal-organic framework materials for metal surface coating from two aspects. One of them is the application of metal-organic framework materials as functional fillers in anticorrosion coatings, including epoxy, acrylic, polyhexylactone, polyvinyl butyraldehyde, polyvinylidene fluoride, and sol-gel coating. The other is the use of the metal-organic framework as the main body of a film layer in a metal anticorrosion coating. Relevant research results show that the metal-organic framework material can largely enhance the protection of metals against corrosion, as functional fillers or conversion films in anticorrosion coatings. Metal-organic framework functional fillers improve the denseness and compatibility of the coating, as ideal containers to load active agents and achieve self-healing, corrosion self-reporting, and other functions. In addition, a metal-organic framework anticorrosion conversion film can be prepared directly on the metal surface to achieve a passive protection (physical barrier effect) and active protection (response to the release of corrosion inhibitors) of the coating. The application of metal-organic framework materials in anticorrosion coatings enhances the corrosion resistance performance and extends the service life of the metal substrate. Although the metal-organic framework film layer and metal-organic framework anticorrosion coating are constantly studied and improved, there are still some technical and controllability problems. First, even though the metal-organic framework conversion film and metal-organic framework anticorrosion coating exhibit ideal corrosion resistances, it is impossible to prepare a metal-organic framework material on a large scale due to the cost and process. Second, different metal-organic framework materials, different metal-organic framework concentrations, different metal substrates, and different process parameters affect the corrosion resistance performance of the metal-organic framework anticorrosion coating. In addition, there are still challenges in maintaining the long-term corrosion resistance of a metal-organic framework material. Therefore, this paper introduces the application of metal-organic framework materials in anticorrosion coatings, and outlines the future development trend. First, the advantages of the metal-organic framework structure and composition should be fully studied. To further improve the loading efficiency of inhibitors, it is necessary to design multiple-response and release-controllable metal-organic framework nanocontainers. Second, the use of novel methods such as machine learning facilitates the screening of proper metal ions and ligands, preparation of metal-organic framework materials with excellent inhibition performances, and investigation on the relevance between the inhibition properties and metal-organic framework structures. With the design of the coating combined with metal-organic framework nanocontainers, properties such as multieffect, long-term effect, and intelligent anticorrosion can be achieved. Third, based on the full application of existing technical methods (in-situ growth, electrospinning, electrochemical deposition, etc.), numerous new methods to prepare a dense metal-organic framework anticorrosion conversion film with a strong adhesion will emerge.

Key words: metal-organic framework corrosion protection anticorrosion coating fillers conversion film