Research progress of superhydrophobic coatings in the field of metal corrosion protection
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摘要: 金属材料凭借其优异的力学性能，在航空航天、海洋工程、交通运输等众多领域具有广泛的应用。然而，金属腐蚀问题仍是制约其在工业领域广泛应用的关键因素之一。研究人员从自然中汲取灵感，通过研究荷叶等动植物表面的微结构，成功设计并开发出具有特殊润湿性能的超疏水表面，将其应用于金属表面后，展现出卓越的抗腐蚀性能。本文回顾了近年来关于超疏水涂层在金属防腐蚀领域的研究成果，归纳了超疏水涂层的耐蚀性和制备技术，阐述了基本润湿理论以及腐蚀防护机制。最后，总结了超疏水涂层在金属防腐蚀领域的研究现状和存在的问题，并对其在金属防腐蚀领域的未来发展趋势和应用前景做了展望。Abstract: With its excellent mechanical properties, metal materials have a wide range of applications in aerospace, marine engineering, transportation and many other fields. However, metal corrosion is still one of the key factors restricting its widespread use in the industrial field. Drawing inspiration from nature, the researchers have successfully designed and developed superhydrophobic surfaces with special wetting properties by studying the microstructure of animal and plant surfaces such as lotus leaves. When applied to metal surfaces, it exhibits excellent corrosion resistance. In this paper, we review the research results of superhydrophobic coatings in the field of metal corrosion protection in recent years, summarize the corrosion resistance and preparation technology of superhydrophobic coatings, and expound the basic wetting theory and corrosion protection mechanism. Finally, the research status and existing problems of superhydrophobic coatings in the field of metal anti-corrosion are summarized, and the future development trend and application prospect of superhydrophobic coatings in the field of metal anti-corrosion are prospected.
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图 2 Young’s方程；(a)固-液-气三者之间的关系；(b)液滴在固体表面的Young’s状态
Figure 2. Young's equation; (a) The relationship between solids, liquids and gases; (b) The Young's state of droplets on solid surfaces
图 4 超疏水在金属表面的防腐蚀机制；(a)Lotus效应[32]；(b)阻碍电化学反应的过程[33]；(c)提高界面结合力[34]；(d)气垫效应保护层[35]
Figure 4. Corrosion protection mechanism of superhydrophobic metal surface; (a) The Lotus effect[32]; (b) Processes that hinder electrochemical reactions[33]; (c) Improve interface binding force[34]; (d) Protective layers of air cushion effect[35]
图 6 (a) Ti合金在NaCl溶液中的腐蚀机制示意图[44]；(b)超疏水双层涂层界面鲁棒性增强的机制以及示意图[47]；(c)腐蚀机制示意图[51]
Figure 6. (a) Corrosion mechanism diagram of Ti alloy in NaCl solution[44]; (b) Mechanism and schematic diagram of enhanced interface robustness of superhydrophobic double-layer coatings[47]; (c) Schematic diagram of corrosion mechanism[51]
图 7 (a)制备碳化硅及其复合涂层的实验方法以及不同涂层的塔菲尔图[62]；(b)超疏水纳米涂层材料涂刷在钢筋的盐雾腐蚀试验和超+疏水纳米涂层材料的热重曲线[70]；(c) BNNP强化抗腐蚀机制图和3 μm与300 nm片径BNNP涂层的阻抗谱[79]
Figure 7. (a) Experimental method for preparing silicon carbide and its composite coating and Tafel diagram of different coatings[62]; (b) Salt spray corrosion test and thermogravimetric curve of superhydrophobic nano-coating material applied to steel bar[70]; (c) BNNP enhanced corrosion resistance mechanism diagram and impedance spectra of 3 μm and 300 nm slice diameter BNNP coatings[79]
图 8 (a) TiO2/PDMS超疏水涂层的制备流程示意图和不同试样在3.5 wt%NaCl溶液中的Tafel曲线以及超疏水涂层防腐蚀机制原理图[107]；(b)盐雾腐蚀不同时间后LDH-F膜的宏观形貌和经不同时间改性后LDH-V-F膜的SEM形貌[110]；(c)不同激光功率刻蚀不锈钢试样表面的接触角和不锈钢电极在NaCl溶液中的极化曲线[117]；(d)EL-1、EL-5、EL-10和EL-15的SEM图像[120]
Figure 8. (a) The preparation process diagram of TiO2/PDMS superhydrophobic coating, the Tafel curve of different samples in 3.5 wt%NaCl solution, and the schematic diagram of the anti-corrosion mechanism of the superhydrophobic coating[107]; (b) The macroscopic morphology of LDH-F film after salt spray corrosion for different time and the SEM morphology of LDH-V-F film after modification for different time[110]; (c) The contact Angle of stainless steel specimen surface and the polarization curve of stainless steel electrode in NaCl solution were etched by different laser power[117]; (d) SEM images of EL-1, EL-5, EL-10 and EL-15[120]
图 9 (a)超疏水膜形成示意图以及电化学测试阻抗图[152]；(b)试样在海水中的极化曲线[156]；(c)镁合金、磷化膜和复合膜在3.5 wt%NaCl溶液中浸泡24 h后的极化曲线以及镁合金和复合膜在3.5 wt%NaCl溶液中浸泡24 h后的腐蚀形貌[161]；(d)吸附了不同浓度LLE聚集材料的Q235钢电极在1 mol/L HCl溶液中的动电位极化曲线[165]
Figure 9. (a) Schematic diagram of superhydrophobic film formation and impedance diagram of electrochemical test[152]; (b) Polarization curve of sample in seawater[156]; (c) Polarization curves of magnesium alloy, phosphating film and composite film after soaking in 3.5 wt%NaCl solution for 24 h and corrosion morphology of magnesium alloy and composite film after soaking in 3.5 wt%NaCl solution for 24 h[161]; (d) Potentiodynamic polarization curves of Q235 steel electrodes adsorbed with different concentrations of LLE aggregates in 1 mol/L HCl solution[165]
表 1 润湿理论在金属防腐蚀方面的潜在优势
Table 1. Potential advantages of wetting theory in metal corrosion protection
Performance Principle Reference Enhanced corrosion resistance Adjusting the wetting properties of metal surfaces can reduce the direct contact between corrosive mediums (such as water, saline solutions, etc.) and the metal surface, thereby delaying the corrosion process of the metal surface [25] Self-cleaning ability Superhydrophobic surfaces can achieve self-cleaning through the lotus effect, thereby reducing the accumulation of dirt and microorganisms, both of which are factors that promote metal corrosion [26] Extended service life By improving the wetting properties of metal surfaces, the durability and service life of metal structures in harsh environments can be enhanced [27] Sustainability Strategies involving the modification of surface wetting properties using physical or chemical methods can be environmentally friendly, providing a sustainable alternative to reducing the use of traditional corrosion inhibitors [28] 
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表 2 不同涂层类型的耐腐蚀性能及其防腐蚀机制
Table 2. Corrosion resistance of different coating types and its anti-corrosion mechanism
Type Materials Evaluation method CA Corrosion mechanism Reference Corrosion resistant superhydrophobic polymer coating Zn-coated carbon steel CA、SEM、EIS 159.8° Resistance to electrochemical corrosion [82] magnesium alloy CA、SEM 152.6° Resistance to electrochemical corrosion [83] Corrosion resistant nano superhydrophobic coating aluminum alloy CA、EIS 162.4° Air cushion effect [84] Galvanized steel CA、XDR 150° Improve interface binding force [85] Steel SEM、EIS 155.4° Lotus effect [86]
Corrosion resistant superhydrophobic ceramic coatingglass ceramics CA、Sanding with sandpaper 158° Air cushion effect [87] rare-earth oxide ceramics CA、SEM 160° Air cushion effect [88]
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表 3 不同制备方法的优缺点以及在金属表面的表征
Table 3. Advantages and disadvantages of different preparation methods and characterization on metal surfaces
Processing method Strengths/Weaknesses Materials CA Reference Self-assembly method Simplicity、Low cost、Versatility、Self-healing ability、Scalability/Structural control difficulties、Stability issues、Complexity and predictability、Scale limitations 6082-T6 Aluminum alloy 180° [137] Sol-gel method Low temperature processes、Uniformity and purity、Controllable microstructure、Diversity、Coating and film preparation/Drying and heat Treatment、Shrinkage and cracking、Reaction time、Complexity、Cost Cu 155° [138] Chemical vapor
depositionHigh-quality films、Wide applicability、Suitable for complex shapes、Good adhesion and interfacial quality、Controllable chemical composition/High-temperature processes、Complex equipment and control、Precursor selection and cost、Environmental concerns、Limited deposition rates Aluminum 158° [139] Laser etching Non-contact process、High accuracy and resolution、Speed and flexibility、Multiple material suitability/Heat affected zone、Equipment cost、Processing time、Possibility of reprocessing 3 Cr13 stainless steel 164° [140] Chemical etching High precision、Wide range of application、High performance/Poor selectivity、Environmental impact、Etching control difficulty Stainless-steel 151.6° [141] Electrochemical etching method Good selectivity、Wide range of applications、Environmentally friendly/Batch processing restriction、Current distribution problem、Equipment and technical requirements Aluminum alloy (152.3±4.5)° [142] Spraying method Simple and practicable、Low cost、Rapid production、Wide applicability/Limited accuracy、Coating thickness control is difficult、Coating thickness control is difficult Q235 Steel plate 163.9° [143] Electrochemical
deposition methodGood uniformity、Environmentally friendly、Precise shape control/High equipment requirements、Limited to conductive substrates、The deposition rate is slow Stainless-steel 160.6° [144]
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