Recent progress in the preparation, properties and applications of superhydrophobic coatings
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摘要: 随着材料工程和涂料工业的发展，具有耐腐蚀、自清洁、防雾、减阻或抗结冰等性能的超疏水涂层由于能够满足不同应用领域的功能需求，越来越受到研究人员的关注。此外，通过进一步在涂层内部引入隔热、防冰、阻燃、防腐等功能填料可赋予其多功能性，极大地拓宽了超疏水涂层的应用领域。本文首先对超疏水涂层的原理进行了梳理；进一步阐述了超疏水涂层的经典润湿理论，包括杨氏模型、Wenzel模型和Cassie-Baxter模型；随后分析了超疏水涂层不同制备方法的特点，并对各方法的优缺点进行了对比；最后通过介绍掺杂功能填料的多功能超疏水涂层研究进展，指出超疏水涂层存在的主要问题，并对其发展方向进行了展望。Abstract: Superhydrophobic coatings with excellent corrosion resistance, self-cleaning, anti-fog, drag reduction, or icing resistance have been paid more and more attention due to their applications in the engineering and coatings industry. In addition, the application of superhydrophobic coatings can be greatly expanded by introducing functional fillers such as heat insulation, anti-icing, flame retardant, and anti-corrosion into the coating. In this paper, the mechanism of superhydrophobic coating is first reviewed, and the classical wetting theory of superhydrophobic coating is further described, including Young's model, Wenzel model, and Cassie-Baxter model. The characteristics of different preparation methods of superhydrophobic coatings are compared, subsequently. Finally, the main problems existing in the development of superhydrophobic coatings are pointed out by introducing the research progress of multifunctional superhydrophobic coatings, and the development direction of superhydrophobic coatings is proposed.
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图 9 (a) ∆G与ri关系图; (b) 临界半径为(ri,c)的冰胚示意图[70]; (c) 液滴温度(20 μL)随时间变化及不同状态下(冷冻过程之前、期间和之后)对应的液滴图片; (d) 在不同状态下(冷冻过程之前、期间和之后)捕获的红外图像[71]
Figure 9. (a) ∆G and ri relationship diagram[70]; (b) Schematic diagram of an ice embryo with a critical radius of (ri,c); (c) Droplet (20 μL) temperature changes over time and corresponding droplet pictures under different states (before, during and after the freezing process); (d) Infrared images captured in different states (before, during and after the freezing process)[71]
图 10 (a) 空白铝基材、SILIKOPHEN AC1000和超疏水(SHP)涂层的冰粘附强度; (b) SHP涂层的结冰/除冰耐久性; (c) 不同温度下样品表面的水接触角; (d) 不同亚冰点温度下样品表面水滴的冻结时间[72]
Figure 10. (a) Ice adhesion strength measurements by push-off and centrifuge tests on bare aluminium, SILIKOPHEN AC1000, and SHP coating; (b) icing/de-icing durability test results for the SHP coating; (c) CA of water droplets on the samples at different temperatures; (d) the freezing time of water droplets on different samples at different sub-freezing temperatures[72]
图 13 (a,b) 超疏水阻燃织物的制备工艺; (c) 未改性PET织物、ASP涂层织物和F-ASP涂层织物的接触角照片; (d) 未改性PET织物, ASP涂层织物和F-ASP涂层织物的垂直燃烧实验照片[86]
Figure 13. (a,b) Preparation process of super hydrophobic flame retardant fabric; (c) Contact Angle photos of unmodified PET fabric, ASP coated fabric and F-ASP coated fabric; (d) Photographs of vertical burning experiments of unmodified PET fabrics, ASP coated fabrics and F-ASP coated fabrics[86]
表 1 超疏水表面制备方法、性能及应用
Table 1. Preparation methods, properties and applications of superhydrophobic surface
Method Process Advantages Disadvantages Substrates Reference Templating method The low surface energy template was prepared, the rough structure of which was replicated, and subsequently removed Easy to process
Low costingStencil removal difficulty Glass
Metal[45-47] Sol-gel method Preparation of homogeneous sol, the sol into gel, remove the solvent in the gel, further solidification gel forming a superhydrophobic material with a specific structure Easy to process
Easy to controllong processing time
Easy to shrinkGlass
Fabric[48-52] Coating method Prepare coating solution and dry after spraying Low costing
Wide application rangePoor adhesion Glass
Metal
Wood
Fabric[53,54] Chemical deposition Through chemical reaction, low surface energy nanoparticles are deposited on the surface of the substrate to form fine and high-performance thin films Easy to process
Strong acid and alkaline resistanceSlow deposition rate
Air pollutionGlass
Wood
Fabric[55-57] Electro-chemical deposition Ions undergo a REDOX reaction under an applied electric field and attach other metal coatings to the surface of one metal by electrodeposition High efficiency
Corrosion resistancePoor adhesion
poor abrasion
Limited in applicationMetal [58-60] Laser etching High energy laser is used to ablate the substrate, which causes a series of reactions under photoelectric or photothermal action and changes the surface roughness of the substrate Easy to control and manipulate
Pollution-freeHigh cost, Glass
Metal[61-65] Chemical etching The glass or metal parts are immersed in an etching solution to obtain the desired etching structure and roughness Easy to process
Low costingPoor uniformity Glass
Metal[66-68] 
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表 2 多功能超疏水涂层
Table 2. Multifunctional superhydrophobic coating
Function Principle Function and application Substrates Reference Anti-icing Inhibit ice cores, prevent frost formation, and reduce ice adhesion Reduce solid surface ice accumulation
Delayed icingSolar panels, cables [69-73] Anticorrosion A physical barrier is constructed between the substrate and the corrosive medium to inhibit interfacial corrosion Improve corrosion resistance of the substrate Ship shell, pipeline [74-76] Self-healing Regeneration of roughness structures, storage and release of healing agents Extended coating life Glass, wood, fabric [77-80] Flame retardant The coating forms a dense coke layer that causes the coated fabric to self-extinguishes during vertical combustion tests Enhance the flame retardancy of the substrate Fabrics, protective materials, furniture [81-86] Thermal insulation Near infrared reflection/shielding Heat insulation and cooling Window glass, outdoor cabinet [87-90]
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