引用本文:王波,辛蕾,张凯,高健,李好,吴连锋.耐久超疏水涂层的制备及其防冰防腐自清洁性能[J].中国表面工程,2024,37(2):238~247
WANG Bo,XIN Lei,ZHANG Kai,GAO Jian,LI Hao,WU Lianfeng.Preparation of Durable Superhydrophobic Coating and Its Anti-icing, Anti-corrosion, and Self-cleaning Properties[J].China Surface Engineering,2024,37(2):238~247
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耐久超疏水涂层的制备及其防冰防腐自清洁性能
王波1, 辛蕾2, 张凯1, 高健2, 李好2, 吴连锋1
1.海洋化工研究院有限公司海洋涂料国家重点实验室 青岛 266071;2.山东科技大学材料科学与工程学院 青岛 266590
摘要:
超疏水涂层在防结冰、防腐蚀等领域具有广阔的应用前景,然而目前仍无法大规模制备稳定的超疏水表面。提出一种操作简单、成本低廉的方法,在铝合金基材上通过一步喷涂法制备出耐磨超疏水涂层。首先在铝合金基体表面涂覆环氧树脂粘结层,待其达到半固化状态时,喷涂硬脂酸修饰的微米 SiO2 和纳米 TiO2 粒子混合悬浮液,固化后该涂层与水的接触角为~ 155.4°,滚动角为~3°,实现了超疏水性。试验结果表明,该超疏水涂层具有较好的耐磨耐久性,在胶带剥离、砂纸摩擦、 紫外光长时间照射以及不同 pH 液滴等多种测试条件下仍具有良好的超疏水性。此外,此超疏水涂层在极端寒冷的天气下可以显著延缓水的冻结时间。环氧树脂和疏水颗粒的协同防腐作用使超疏水涂层在海水中表现出良好的防腐蚀性能。所制备的超疏水涂层还具有优异的自清洁特性,且因 TiO2 粒子本身的光降解性能,该涂层还可用于光降解污染物和净化水质。这种简单、环保的超疏水涂层在防结冰、防腐蚀等方面具有潜在的应用前景,可为克服传统超疏水表面使用耐久性差的问题提供解决思路。
关键词:  超疏水  喷涂法  防结冰  防腐蚀  光降解
DOI:10.11933/j.issn.1007-9289.20230310002
分类号:TG156;TB114
基金项目:海洋涂料国家重点实验室开放课题(GZ-21-006);国家自然科学基金(51905315)
Preparation of Durable Superhydrophobic Coating and Its Anti-icing, Anti-corrosion, and Self-cleaning Properties
WANG Bo1, XIN Lei2, ZHANG Kai1, GAO Jian2, LI Hao2, WU Lianfeng1
1.State Key Laboratory of Marine Coatings, Marine Chemical Research Institute, Co.Ltd., Qingdao 266071 , China;2.School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 , China
Abstract:
Aluminum alloys are widely used in ships and offshore platforms owing to their high fatigue strength, excellent corrosion resistance, welding performance and cold workability. Although the surface of the aluminum alloy usually forms an oxide film in natural environments, the film is thin and can easily be damaged during application, resulting in damaging the substrate. Therefore, preparing anti-icing, anti-corrosion and self-cleaning superhydrophobic coatings on aluminum alloy substrates is important for improving their performance and expanding their application fields. Superhydrophobic surfaces are with a water contact angle exceeding 150° and a roll-off angle below 10°. Inspired by superhydrophobic surfaces of nature, researchers have successfully prepared and developed various artificial superhydrophobic coatings that can be applied in various fields, such as self-cleaning, anti-corrosion, and anti-icing. To date, many methods for preparing superhydrophobic coatings with micro-nano structures and low-surface-energy, such as spraying and electrodeposition, have been proposed. However, currently prepared superhydrophobic coatings are highly susceptible to damage because their rough surface morphology is easily damaged by mechanical wear, weak adhesion to the substrate, and poor resistance to harsh conditions, which seriously affects their large-scale application. Therefore, improving the wear resistance of superhydrophobic coatings is an urgent issue. For the micro-nanocomposite structures on superhydrophobic surfaces, the single micron-scale structure protects fragile and functional nanoscale structures because of its ability to withstand more frictional loads than nanoscale structures. Epoxy is a thermosetting resin, and its highly cross-linked three-dimensional network structure endows it with excellent bonding and adhesion performance. The use of sturdy adhesives, such as epoxy resin, to improve the adhesion between the coating and substrate. Moreover, spraying modified micro-nanocomposite particles to create micro-nanostructures is an effective strategy for the large-scale preparation of wear-resistant superhydrophobic coatings. Therefore, in this study, a simple and cost-effective method to prepare a dual-scale durable superhydrophobic coating on an aluminum alloy substrate by one-step spraying of micro / nano mixed particles is proposed. First, an epoxy resin adhesive layer was applied to the surface of the aluminum alloy substrate, after it reached a semi-cured state, a mixed suspension of stearic acid-modified micro SiO2 and nano TiO2 particles was sprayed. After curing, the contact angle between the coating and water was ~155.4° and the roll-off angle was ~3°, indicating excellent superhydrophobicity. The prepared coating surface shows an obvious micro-nanostructures, also modified by low-energy substances, which indicates microstructure and composition conditions for constructing superhydrophobic surfaces. The prepared superhydrophobic coating exhibited strong adhesion on substrate, excellent wear resistance and durability, also with good superhydrophobicity under various tests, including 19 times of tape peeling, 20 cm of sandpaper wear, long-term exposure to ultraviolet light, and droplet testing at different pH. The prepared superhydrophobic coating significantly delayed the freezing time of water in extremely cold weather by approximately eight times that of the substrate. Simultaneously, the synergistic anti-corrosion effect of the epoxy resin and superhydrophobic property caused the prepared coating to exhibit excellent anti-corrosion performance in seawater. In addition, the prepared superhydrophobic coating shows excellent self-cleaning performance, and can be used for the photodegradation of pollutants and purification of water because of the photodegradation performance of TiO2 particles. This simple and environmentally friendly superhydrophobic coating is promised to apply in anti-icing, anti-corrosion and other aspects, and provides a solution for improving the durability of traditional superhydrophobic surfaces.
Key words:  superhydrophobic  spraying method  anti-icing  anti-corrosion  light degradation
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