Research progress of graphene oxide composite coatings in metal corrosion protection
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摘要: 氧化石墨烯(GO)作为石墨烯的衍生物具有优异的综合性能,在金属的防腐蚀领域中表现出了巨大的应用潜力。GO不仅具有石墨烯的二维层状结构,还含有羟基、羰基、羧基和环氧基团等官能团可作为活性位点与其他物质进行共价/非共价性功能化改性,因此氧化石墨烯常被用作填料来增强涂层的综合性能。本文以氧化石墨烯复合涂层为中心,简要的介绍了其理化性质,从当前世界金属腐蚀的情况和腐蚀类型为切入点,针对一些常用的腐蚀防护方法进行了讨论。综述了近年来国内外关于氧化石墨烯与有机物和无机物的复合涂层在金属腐蚀与防护领域的研究进展并对复合涂层的防腐机制进行了简述;最后,总结了目前研究工作中存在的关键科学难题与挑战,对涂层的研究方向与应用前景进行了展望。Abstract: As a derivative of graphene, graphene oxide (GO) has excellent comprehensive performance, showing great application potential in metal corrosion and protection. Graphene oxide has not only a two-dimensional layered structure but also contains hydroxyl, carbonyl, carboxyl, epoxy groups and other functional groups that can be used as active sites with other substances for covalent/non-covalent functionalization modification, so graphene oxide is often used as a filler to enhance the comprehensive performance of coatings. This paper reviews the recent research progress on graphene oxide composite coating in metal corrosion and protection. The first part summarizes the morphology of metal corrosion and the corrosion protection methods, explains the primary forms of metal corrosion, and discusses the current main metal corrosion protection methods. The second part introduces the physicochemical properties of graphene and its derivatives. In this paper, graphene oxide (GO) is the main focus. It has tremendous application potential in metal corrosion protective coatings due to its sheet structure, excellent dispersion, and abundant oxygen-containing functional groups on the surface, which are the active point of the reaction and easy modification. The third part introduces the current GO composite coating, which compares the corrosion resistance of traditional coatings, GO organic/inorganic unit composite coatings and GO multi-composite coatings. It was found that the performance of GO multi-component composite coating is far better than that of GO organic/inorganic unit composite coating and traditional coating. This is due to the excellent dispersion of GO, which enables it to fill the pores that occur during the curing and film-forming process of organic polymer materials and improve the corrosion resistance of the coating. The photogenic cathodic protection mechanism and current situation of GO anti-corrosion coating are introduced, and due to the green environmental protection and excellent anti-corrosion effect, it is regarded as the future development trend of GO composite coating. The fourth part summarizes the key scientific issues and challenges of GO composite anti-corrosion coating in the current research. It looks forward to the research direction and application prospect of GO composite anti-corrosion coating.
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图 5 GO/Mn-Zn2SiO4材料的腐蚀防护机制图[43](光生阴极效应(a)、无机锰离子磁感应效应(b)、二维GO屏蔽效应(c)、阴极二次保护效应(d))
Figure 5. Corrosion protection mechanism of GO/Mn-Zn2SiO4 material [43]. (Photogenerated cathode effect (a), inorganic manganese ion magnetic induction effect (b), two-dimensional GO shielding effect (c), cathode secondary protection effect (d))
表 1 GO作为涂层填料相对于其他常见无机填料的优缺点
Table 1. Advantages and disadvantages of GO as a coating filler over other common inorganic fillers
Type Character Advantages Disadvantages GO 1. High specific surface area, good mechanical properties, excellent barrier and shielding properties;
2. Excellent response reactivity, thermal and chemical stabilities;
3. Oxygen-containing functional group can serve as active sites for reactions; hydrophilic groups on the surface are more easily modified by polymers or alkali metal oxides;
4. "Maze effect" can increase the diffusion path of the corrosion factor in the coating, and has a high resistance to permeability.1. Easy to agglomerate, dispersibility and stability are reduced after agglomeration;
2. Electrical conductivity, prone to galvanic coupling corrosion at locations of coating defects.Nano-ZnO 1. High melting point;
2. Good oxidation and corrosion resistance.1. High surface activity, easy to agglomerate and lose the special effect of nanoparticles after agglomeration;
2. Hydrophilic and oleophobic, poor dispersibility and stability in organic media;
3. Weak bonding with the substrate, poor interfacial compatibility, easy to produce voids, micro-cracks and other interfacial defects.Nano-Al2O3 1. High strength, thermal conductivity and wear resistance;
2. Excellent electrical insulation;
3. Stable physical and chemical properties.1. Poor compatibility with the substrate, poor dispersion, easy to agglomerate;
2. Functionalisation of the surface may lead to a reduction in filler size, resulting in defects on the surface;
3. Different shapes and sizes also have an effect on the corrosion resistance of the coating.Micro/Nano-SiO2 1. High hardness, high mechanical strength;
2. Excellent thermal and chemical stability;
3. Low density, small particle size, large specific surface area;
4. Colorless, odorless and pollution-friendly;
5. Good corrosion resistance.1. Fine particles and high hydrophilicity, easy to agglomerate;
2. The coating is prone to cracking during curing and reducing the corrosion resistance of the coating. -
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