摘要
目的 实现电沉积镀层表面微纳分级结构的简单构筑,赋予其优异的超疏水特性。方法 以氯化胆碱-尿素低共熔溶剂为溶剂,加入一定比例的氯化镍和硬脂酸溶解后得到电解液,通过调节电沉积时间得到一系列不同形貌的硬脂酸镍镀层。利用SEM、FTIR和XPS等表征技术研究了沉积时间对所制备镀层形貌和组成的影响,利用接触角测量仪探究了不同形貌硬脂酸镍的超疏水性和化学稳定性,利用电化学工作站考察了超疏水镀层的耐腐蚀性。结果 在低共熔溶剂中通过一步电沉积法得到不同形貌结构的硬脂酸镍镀层,其表面形貌与沉积时间密切相关。沉积初期呈现纳米片状结构,随着沉积进行,硬脂酸镍纳米片逐渐堆积、交叉,最终形成花状微纳分级结构。得益于其独特的微纳分级结构和自身低表面能特性,花状硬脂酸镍镀层不仅具有优异的超疏水性(θWCA=(157.3±1.9)°,θSA=(3.6±1.1)°)和自清洁特性,还对强酸、强碱以及盐溶液表现出优异的化学稳定性。与纳米片状和零散花状的硬脂酸镍相比,花状微纳分级结构的硬脂酸镍的耐腐蚀性(Jcorr=1.75×10?6 A/cm2)分别提高了20倍和7倍。结论 以低共熔溶剂为电解液,通过控制沉积时间可实现镀层表面微纳分级结构的调控与构筑,进而获得性能优异的超疏水镀层。
Abstract
In this work, a template free one-step electrodeposition method in deep eutectic solvent (DES) was reported for the preparation of hierarchical structured superhydrophobic surface with excellent chemical stability, corrosion resistance and self-cleaning properties. It is well known that, surface hierarchical structures and surface free energy are the main factors for preparation of superhydrophobic surfaces. To fabricate the superhydrophobic surface with micro/nano hierarchical structures by one-step electrodeposition, in this paper, the choline chloride-urea deep eutectic solvent (ChCl-Urea DES) containing 0.04 mol/L NiCl2.6H2O and 0.1 mol/L stearic acid was used as electrolyte. A series of nickel stearate (Ni[CH3(CH2)16COO]2) coatings with different surface morphologies were obtained on the copper substrate by regulating the electrodeposition time (These coatings were named NS-1, NS-2 and NS-3 based on the deposition time, respectively). The surface morphology and chemical composition of the as-prepared coatings were characterized by a scanning electron microscope (SEM), an X-ray energy dispersive spectroscopy (EDS), a Fourier-transform infrared spectroscopy (FT-IR) and an X-ray photoelectron spectroscopy (XPS). The water contact angles, chemical stability, corrosion resistance and self-cleaning of the as-prepared coatings were investigated by a water contact angle measurement and electrochemical workstation. The results showed that the component of the as-prepared coatings was nickel stearate, and the surface morphologies of the coatings were closely correlated with the deposition time. In the initial stage, nickel ions (Ni2+) reacted with stearate ions (CH3(CH2)16COO?) to form nano sheet-shape nickel stearate on the surface of copper substrate. As the deposition time increased, the nano sheets gradually increased and interconnected each other, eventually formed micro-scale flower-like structures. So, the surface morphology of nickel stearate changed from uniform nano sheets (10 min) to scattered flower-like structures (30 min), and finally to uniform and dense flower-like structures (50 min). The wetability test showed that the water contact angle (θWCA) of NS-1 with nano sheet-like structures was only about (130.7±2.2)°. The θWCA of scattered flower-like NS-2 was improved to (147.8±2.5)° due to the increase of surface roughness. The NS-3 exhibited desirable superhydrophobicity with a θWCA of (157.3±1.9)° and a θSA of (3.6±1.1)° when the surface was covered by uniform and dense hierarchical micro/nano-scaled flower-like structures. Furthermore, different kinds of droplets (such as tea, methylene blue solution, methyl orange solution, milk, NaCl solution and coke) on NS-3 surface maintained a spherical shape with the WCAs ranging between 154.3° and 156.5°, indicating that the NS-3 surface had excellent superhydrophobicity and antifouling properties. Clearly, the coarse hierarchical structure had a better ability to trap a large amount of air and improve the superhydrophobicity compared with the nano sheet-like structure. The stability test found that WCA of the superhydrophobic NS-3 coating maintained larger than 152.1° and the RAs values maintained lower than 7° when the pH values ranged from 1 to 14, indicating that pH had little effect on the WCAs. The NS-3 coating still possessed good superhydrophobic performance with a WCA of 151.8° after soaking for 8 days in 3.5wt.% NaCl solution. These phenomena indicated that the superhydrophobic NS-3 coating had outstanding chemical stability. Tafel tests showed that the Jcorr of NS-3 superhydrophobic surface were 1.75×10?6 A/cm2, which was decreased about 7 and 20 times, respectively, in comparison with NS-2 and NS-1. For the self-cleaning test, the spherical droplets quickly rolled off and took away the surface contaminants (such as graphite powder, SiO2 powder and SiC powder). It could be anticipated that the micro/nano hierarchical structured NS-3 showed excellent superhydrophobicity, self-cleaning, chemical stability and corrosion resistance. Using deep eutectic solvent as the electrolyte provides a promising method to fabricate micro/nano hierarchical structured superhydrophobic surface by one-step electrodeposition method.
关键词
低共熔溶剂;电沉积;硬脂酸镍;微纳分级结构;超疏水;耐腐蚀;自清洁
Key words
deep eutectic solvent; electrodeposition; nickel stearate; micro/nano hierarchical structure; superhydrophobicity; corrosion resistance; self-cleaning
李梦情, 崔偎偎, 白子龙, 徐银杏, 于会珠, 李瑞乾.
低共熔溶剂中超疏水结构的一步电沉积制备及性能研究[J]. 表面技术. 2023, 52(9): 331-339
LI Meng-qing, CUI Wei-wei, BAI Zi-long, XU Yin-xing, YU Hui-zhu, LI Rui-qian.
One-step Electrodeposition and Performance of Superhydrophobic Structure from Deep Eutectic Solvent[J]. Surface Technology. 2023, 52(9): 331-339
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基金
国家自然科学基金(52101080);安徽高校优秀青年科研项目(2022AH030132);安徽省自然科学基金(2008085QE201、2008085QB54);安徽省高校自然科学研究项目(KJ2020A0537、2022AH051316);阜阳师范大学青年人才重点项目(rcxm202207、2017KYQD0009);大学生创新创业项目(202110371003、S202210371045)