表面技术第52卷第11期硫醇改性超疏水铜表面的耐候性及失效机理杜文倩1，王德辉1,2，余华丽1，李罗慧子1，罗静1，邓旭1*（1.电子科技大学 基础与前沿研究院，成都 610054；2.中国空气动力研究与发展中心 结冰与防除冰重点实验室，四川 绵阳 621000）摘要：目的探究户外环境中导致硫醇改性超疏水铜表面失效的因素及其超疏水性失效的机制。
方法通过化学刻蚀法在铜表面构筑纳米结构，利用正十二硫醇进行表面改性，得到具有超疏水性的铜表面。
将该表面置于户外进行耐候性研究，并通过4种模拟户外环境实验探究超疏水性失效的原因，包括组合循环实验（循环条件含紫外辐射、淋雨和凝露）、紫外辐射实验、水环境实验和温度实验。
结果超疏水铜表面经过10 d的户外实验后，其接触角由初始状态的158.5°降至131.1°，表明该表面的超疏水性能已失效。
经过2次组合循环实验（每次循环的时间为12 h）、20 d紫外辐射实验及30 d水环境实验后，该表面的接触角分别降至130.3°、124.5°、131.7°，表明该表面均已失去超疏水性；经过40 d高温实验后，表面的超疏水性开始失效。
XPS谱图表明，在超疏水性失效后该表面不存在硫元素，即正十二硫醇已经脱离表面。
结论超疏水铜表面的硫醇分子脱落是超疏水性失效的根本原因。
紫外辐射、水和高温是导致超疏水铜表面超疏水性失效的主要因素。
其中，紫外辐射或水对超疏水性的破坏速度比高温快。
相较于单一因素（紫外辐射、水或高温），三者的协同作用更加速了硫醇分子从表面的脱落，导致超疏水性失效的速度更快。
关键词：超疏水铜表面；化学刻蚀法；硫醇改性；环境耐候性；超疏水性失效；失效机理中图分类号：TG17；TB34 文献标识码：A 文章编号：1001-3660(2023)11-0326-09DOI：10.16490/ki.issn.1001-3660.2023.11.027Weather Resistance and Failure Mechanism of SuperhydrophobicCopper Surface Modified by MercaptansDU Wen-qian1, WANG De-hui1,2, YU Hua-li1, LI Luo-hui-zi1, LUO Jing1, DENG Xu1*(1. Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China,Chengdu 610054, China; 2. Key Laboratory of Icing and Anti/De-icing, China Aerodynamics Research andDevelopment Center, Sichuan Mianyang 621000, China)ABSTRACT: The superhydrophobic copper surface has a very broad application prospect in the fields of self-cleaning, anti-frost, anti-corrosion, reduction of resistance and residue of fluid in copper pipes, etc. However, the weather resistance of the superhydrophobic copper surface in the real application environment is not clear, and there is still short of systematic research.Therefore, the work aims to explore the failure factors of mercaptan modified superhydrophobic copper surface in outdoor environment and the mechanism of superhydrophobic failure. The nanostructure was constructed on the copper surface by收稿日期：2022-11-15；修订日期：2023-02-08Received：2022-11-15；Revised：2023-02-08基金项目：中国空气动力研究与发展中心结冰与防除冰重点实验室开放课题（IADL20210411）Fund：Key Laboratory of Icing and Anti/De-icing of CARDC (IADL20210411)引文格式：杜文倩, 王德辉, 余华丽, 等. 硫醇改性超疏水铜表面的耐候性及失效机理[J]. 表面技术, 2023, 52(11): 326-334.DU Wen-qian, WANG De-hui, YU Hua-li, et al. Weather Resistance and Failure Mechanism of Superhydrophobic Copper Surface Modified by Mercaptans[J]. Surface Technology, 2023, 52(11): 326-334.*通信作者（Corresponding author）第52卷第11期杜文倩，等：硫醇改性超疏水铜表面的耐候性及失效机理·327·chemical etching, and then the surface was modified with 1-dodecanethiol to obtain a superhydrophobic copper surface (SCS).The SCS was placed outdoors to study its weather resistance. The mechanism of failure was explored by four kinds of experiments simulating outdoor conditions. Simulation experiments included combinatorial cycle experiment (cyclic conditions including UV radiation, rain and condensation), UV radiation experiment, water environment experiment and temperature experiment ("high temperature" in this work referred to the high temperature in the outdoor environment). The mechanism of superhydrophobicity failure of SCS was verified by the environmental weather resistance of hydrophobic copper surface (HCS) without rough microstructure. Scanning electron microscope (SEM), contact angle measurement and X-ray photoelectron spectrometer (XPS) were used to characterize the morphology, wettability and chemical composition of SCS, respectively. After10 days of outdoor experiments, the water contact angle of SCS was reduced from the initial 158.5° to 131.1°. According to theSEM diagram and Energy Dispersive Spectrometer (EDS) analysis, impurities containing metal/non-metal inorganic substances and organic matter were absorbed on the surface. The experimental results showed that the superhydrophobic performance of SCS failed and the self-cleaning performance was also lost. The water contact angle of SCS decreased to 130.3°, 124.5° and 131.7° after 2 combinatorial cycle experiments (12 hours of each cycle), 20 days of UV radiation experiment, and 30 days of water environment experiment respectively, indicating that SCS lost its superhydrophobic property. After 20 days of high temperature experiment, SCS still maintained superhydrophobic property, but the superhydrophobic property began to fail after40 days of high temperature experiment. XPS spectrum indicated that sulfur element was no longer present on SCS after thefailure of superhydrophobic properties, i.e. 1-dodecanethiol was removed from SCS. The shedding of mercaptan molecules on the SCS was the root cause of superhydrophobic failure.UV radiation, water and high temperature were the main factors leading to the failure of superhydrophobicity of SCS. The superhydrophobic property of SCS was destroyed faster by UV radiation or water than by high temperature. Compared with the effect of a single factor (UV radiation, water or high temperature), the synergistic effect of the three accelerated the shedding of mercaptan molecules from SCS, thereby accelerating the rate of superhydrophobic failure.By studying the weather resistance and failure mechanism of HCS, it is found that the wettability change trend of HCS is consistent with that of SCS, and the hydrophobicity failure of HCS without rough microstructure is also caused by the shedding of mercaptan molecules on the surface. The results verify that the mercaptan molecule detachment from the surface results in the superhydrophobic failure of SCS.KEY WORDS: superhydrophobic copper surface; chemical etching method; mercaptan modification; environmental weather resistance; superhydrophobic failure; failure mechanism超疏水表面在自清洁[1-6]、防腐[7-8]、防结冰[9-10]、防雾[11-12]、集水[13]、减阻[14]、液滴操控[15]及生物医学[16]等领域展现出广阔的应用前景，引起了研究人员的广泛关注。
