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化学进展 2021, Vol. 33 Issue (9): 1525-1537 DOI: 10.7536/PC210216 前一篇   后一篇

• 综述 •

耐久型超疏水表面:理论模型、制备策略和评价方法

曹祥康1, 孙晓光2, 蔡光义1, 董泽华1,*()   

  1. 1 华中科技大学化学与化工学院 材料化学与服役失效湖北省重点实验室 武汉 430074
    2 中车青岛四方机车车辆股份有限公司 青岛 266111
  • 收稿日期:2021-02-20 修回日期:2021-05-05 出版日期:2021-09-20 发布日期:2021-09-06
  • 通讯作者: 董泽华
  • 基金资助:
    国家自然科学基金项目(51371087); 国家自然科学基金项目(51771079); 中车青岛四方机车车辆股份有限公司项目(SF/JG-吕字-2020-50)
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Durable Superhydrophobic Surfaces: Theoretical Models, Preparation Strategies, and Evaluation Methods

Xiangkang Cao1, Xiaoguang Sun2, Guangyi Cai1, Zehua Dong1()   

  1. 1 Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology,Wuhan 430074, China
    2 CRRC Qingdao Sifang Co., Ltd, Qingdao 266111, China
  • Received:2021-02-20 Revised:2021-05-05 Online:2021-09-20 Published:2021-09-06
  • Contact: Zehua Dong
  • Supported by:
    National Natural Science Foundation of China(51371087); National Natural Science Foundation of China(51771079); CRRC Qingdao Sifang Co., Ltd(SF/JG-吕字-2020-50)

超疏水材料以其独特的润湿性在日常生活和工业领域都展示出广阔的应用前景,但其表面的微纳米结构和低表面能物质易受到机械摩擦或化学侵蚀而失去超疏水性。当前诸多报道都采用微纳结构设计和表面优化来延长超疏水材料的耐久性,以期提升其商业价值。本文先从表面浸润模型出发,包括经典理论、亚稳态理论和接触线理论,梳理了超疏水理论模型的发展脉络,阐明这些理论在超疏水耐久性设计上发挥的关键指导作用。接着对微纳米结构设计、胶黏+涂装、铠装防护、自修复和气膜修补等延长超疏水耐久性的制备策略进行了总结,并对不同制备策略各自的优势和局限性进行简要评述。本综述还从机械稳定性和化学稳定性两方面汇总了超疏水耐久性的快速评价手段,讨论了提升超疏水表面耐久性所遇到的问题,并展望了超疏水材料的发展前景,以期助力长效超疏水材料的研发和应用。

关键词： 超疏水, 耐久性, 理论模型, 制备策略, 评价手段

Superhydrophobic surface has broad applications in daily life and industries owing to its unique wettability. However, the micro-nano structures and low surface energy substance of surface are vulnerable to mechanical damage and chemical erosion, often prone to lose their superhydrophobicity. It is of great practical significance to construct durable superhydrophobic surface through morphologic design and performance optimization for its commercialization. In this review, based on the surface wettability model, including classical theory, metastable theory and contact line theory, the development history of superhydrophobic theoretical model is first reviewed, as well as their key guiding roles in the design of superhydrophobic durability. Then, the preparation strategies for durable superhydrophobic surface, such as micro-nano structure design, adhesive + coating, armor protection, self-healing, air cushion replenishment or replacement, are summarized. And the advantages and limitations of each strategy are reviewed. In addition, according to mechanical and chemical stability, the evaluation methods of superhydrophobic durability are illustrated. Finally, the problems and prospects of durable superhydrophobic surface are summarized for the future research of durable superhydrophobic coating.

Contents

1 Introduction

2 Theoretical model of wettability

2.1 Classical wetting theory

2.2 Metastable wetting theory

2.3 Contact line theory

3 Preparation strategy of durable superhydrophobic surface

3.1 Micro-nano structure regulation

3.2 Adhesive + coating

3.3 Armor protection

3.4 Self-healing policy

3.5 Air cushion replenishment or replacement

4 Evaluation methods for durable superhydrophobic surface

4.1 Mechanical durability

4.2 Chemical durability

5 Existing problems

6 Conclusion and outlook

Key words: superhydrophobic, durability, theoretical model, preparation strategies, evaluation methods
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图1 固体表面润湿状态示意图:(A)液滴平衡状态下的表面张力;(B)Wenzel状态;(C)Cassie状态
Fig.1 Schematic diagram of the solid surface wetting state: (A) Surface tension in the equilibrium state of the droplet; (B) Wenzel state; (C) Cassie state
图2 激光共聚焦显微镜记录超疏水表面亚稳态在不同条件下的可视化动态形成过程[20]:在(A) 0 kPa、(B) 14 kPa、 (C) 50 kPa下浸泡5 min; (D) 50 kPa下浸泡15 min
Fig.2 Visualized dynamic formation process of metastable state of superhydrophobic surface by confocal microscopy[20]. after 5 min immersion under (A) 0 kPa; (B)14 kPa; (C) 50 kPa; and (D)15 min immersion under 50 kPa
图3 超疏水表面微结构设计示意图及实际SEM形貌[39]
Fig.3 Schematic diagram of the microstructure design of super-hydrophobic surface and the actual SEM morphology[39]
图4 有机/无机复合超疏水涂层制备示意图[48]
Fig.4 Schematic diagram of preparation of organic/inorganic composite superhydrophobic coating[48]
图5 铠装超疏水表面的制备示意图[51]
Fig.5 Preparation schematic diagram of armored super-hydrophobic surface[51]
图6 室温下硅油自补充修复表面低表面能物质示意图[53]
Fig.6 Schematic diagram of silicone oil self-replenishment repair for low surface energy substances at room temperature[53]
图7 在高温刺激下自修复表面微纳米粗糙形貌示意图[56]
Fig.7 Diagram of self-repairing micro-nano rough morphology of surface under high temperature stimulation[56]
图8 加热和酸性刺激下微纳米结构和低表面能物质双自修复示意图及实际修复效果[46]
Fig.8 Schematic diagram of the dual self-repair of micro-nano structures and low surface energy substances under heating and acid stimulation as well as the actual repair effect[46]
图9 三维超疏水表面:(A~E)制备示意图及SEM形貌[63]
Fig.9 Three-dimensional superhydrophobic surface: (A~E) Schematic diagram of block preparation and SEM morphology[63]
图10 气体补充促进Wenzel状态向Cassie状态转变过程[66]
Fig.10 Gas supplementation promotes the transition from Wenzel state to Cassie state[66]
图11 超疏水表面机械稳定性的评价方法. (A) 摩擦磨损;(B)胶带剥离; (C) 水流冲击
Fig.11 Evaluation methods of mechanical stability of superhydrophobic surface. (A) Friction and wear; (B) Tape peeling; (C) Water impact
表1 不同制备策略下超疏水表面抗磨损和耐酸碱性能比较
Table 1 Comparison of wear resistance and acid and alkali resistance of superhydrophobic surface under different preparation strategies
Preparation strategies Surfaces Abrasion test Acid-base solution immersion ref
Load(kPa) Friction distance(cm) pH range Immersion time(h)
Micro-nano structure
design		 PDMS 10 1000 1~13 80 101
Copper 1.2 200 102
Adhesive + coating TiO2 1.3 400 44
PVDF/FEVE/GO@TiO2 3.42 28 000 1~14 72 103
Al2O3/Epoxy 5 20 000 49
PTFE-CP&MgO-AOP 2.6 10 000 1~14 100
PDMS@ZnSn(OH)6 2.2 300 2~13 28 6
QAS@SiO2 1~13 168 30
SiO2/B-Epoxy 1.6 2160 1~14 12 85
Armor protection Metal/glass/ceramic 12 000 10 000 aqua regia 4 50
ADP/Copper 1~14 24 104
Self-healing SiO2/Epoxy 7.5 1150 1~14 0.5 105
SiO2/PDMS 5 10 000 62
SiO2/F-Epoxy 12.25 50 000 63
PTFE/F-Epoxy 5 1000 aqua regia 1 64
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