Surface structuration (micro and/or nano) governed by the fluorinated tail lengths toward superoleophobic surfaces

As compared to superhydrophobic surfaces, the challenge to obtain superoleophobic properties, surfaces against low-surface-tension probe liquids such as hexadecane, is very important because of their high tendency to wet. From the molecular design of the monomer, it is possible to obtain in one step superoleophobic surfaces by electrodeposition. Hence, we report the synthesis and the characterization of an original series of fluorinated 3,4-ethylenedioxypyrrole (EDOP) derivatives. The electrodeposited polymer films are characterized by contact angle measurements (static and dynamic with various probe liquids), optical profilometry, and scanning electron microscopy. In the view toward reaching superoleophobic properties, a common approach is to increase the number of fluoromethylene units of the surface post-treatment agent. Here, surprisingly, it is possible, in one step, to reach more efficient antioil surface properties by decreasing the length of the fluorinated tail (F-octyl to F-hexyl). This fact can be explained by a double scale of structuration (micro and nano) induced using only F-hexyl tails.     

超疏水性表面的制备及应用进展

近年来,受荷叶、水黾腿、壁虎脚等天然超疏水生物表面特性的启发,研究者们进行了大量仿生超疏水表面材料的制备及应用研究。超疏水性表面因其特殊的微纳分层结构,具有自清洁、防覆冰、防腐蚀、减阻等优异性能。本文阐述了表面润湿、疏水的基本机理,以及超疏水表面研究的理论基础,对超疏水表面制备的最新研究进展进行了综述,并揭示了研究中存在的问题。最后,介绍了超疏水表面在涂料、织物、防腐、抗菌及防雾等领域中的应用,展望了其未来的研究方向和前景。     

From superamphiphobic to amphiphilic polymeric surfaces with ordered hierarchical roughness fabricated with colloidal lithography and plasma nanotexturing

Ordered, hierarchical (triple-scale), superhydrophobic, oleophobic, superoleophobic, and amphiphilic surfaces on poly(methyl methacrylate) PMMA polymer substrates are fabricated using polystyrene (PS) microparticle colloidal lithography, followed by oxygen plasma etching-nanotexturing (for amphiphilic surfaces) and optional subsequent fluorocarbon plasma deposition (for amphiphobic surfaces). The PS colloidal microparticles were assembled by spin-coating. After etching/nanotexturing, the PMMA plates are amphiphilic and exhibit hierarchical (triple-scale) roughness with microscale ordered columns, and dual-scale (hundred nano/ten nano meter) nanoscale texture on the particles (top of the column) and on the etched PMMA surface. The spacing, diameter, height, and reentrant profile of the microcolumns are controlled with the etching process. Following the design requirements for superamphiphobic surfaces, we demonstrate enhancement of both hydrophobicity and oleophobicity as a result of hierarchical (triple-scale) and re-entrant topography. After fluorocarbon film deposition, we demonstrate superhydrophobic surfaces (contact angle for water 168°, compared to 110° for a flat surface), as well as superoleophobic surfaces (153° for diiodomethane, compared to 80° for a flat surface).     

Preparation of novel methyl methacrylate/fluorinated silsesquioxane copolymer film with low surface energy

Random copolymers of methyl methacrylate and fluorinated polyhedral oligomeric silsesquioxane (F-POSS) were synthesized and the corresponding thin films were prepared from solvent casting. Their microstructure was confirmed by ¹H NMR, elemental analysis and GPC. Separation occurs in the bulk of the film during solvent evaporation which can be evidenced by Transmission Electron Microscopy, TEM, with POSS-rich nanophase sizes from 20 to 50 nm. Nanostructuration is attributed to the self-assembly of F-POSS due to the cluster-cluster interactions resulting from the nature of their ligands, i.e., cycloaliphatic ligands and perfluorinated chains. Thermogravimetric analysis was used to investigate the thermal degradation temperature. It was shown that when F-POSS content is higher than 2.8 mol%, the incorporation of F-POSS could improve the thermal stability of PMMA significantly. In addition, it was shown that these fluorinated POSS-based copolymer surfaces could reduce the surface energy and could be used to design water-repellant nanocomposite coatings.

     

Facile synthesis of hydrophobic fluoroalkyl functionalized silsesquioxane nanostructures

New fluorinated polyhedral oligomeric silsesquioxane (F-POSS) structures possessing a high degree of hydrophobicity have been prepared via a facile corner-capping methodology.     

Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil

We demonstrate that superhydrophobic and superoleophobic nanocellulose aerogels, consisting of fibrillar networks and aggregates with structures at different length scales, support considerable load on a water surface and also on oils as inspired by floatation of insects on water due to their superhydrophobic legs. The aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Furthermore, we demonstrate high-adhesive pinning of water and oil droplets, gas permeability, light reflection at the plastron in water and oil, and viscous drag reduction of the fluorinated aerogel in contact with oil. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.     

Hydrocarbon versus fluorocarbon in the electrodeposition of superhydrophobic polymer films

To elaborate on superhydrophobic surfaces, we report the electrochemical synthesis, surface morphology, and wettability of hydrocarbon conductive polymer films obtained by the electrodeposition of polythiophene, poly(3,4-ethylenedioxythiophene) (i.e., PEDOT), and poly(3,4-ethylenedioxypyrrole) (i.e., PEDOP) derivatives. Highly hydrophobic films were obtained from n-C(14)H(29) and n-C(8)H(17) chains in the cases of polythiophenes and PEDOP, respectively. By contrast, superhydrophobic films were formed by the deposition of PEDOT substituted with n-C(10)H(21) chains (PEDOT-methyl undecanoate): static contact angle ≈ 160.6°, hysteresis ≈ 2°, and sliding angle ≈ 3°. Their surface properties were compared to those of previously reported fluorinated analogues. The water-repellent properties of PEDOT-methyl undecanoate were similar to the best surface properties obtained with fluorinated monomers. Even if the main approach for the chemical factor to build up superhydrophobic surfaces is via a coating of a fluorinated compound, this work confirms that the formation of fractal surfaces is able to achieve super-anti-wetting properties within a hydrocarbon series (less expensive with a favorable ecotoxic approach), and it opens a new path to bioinspired surfaces.     

Fabrication, surface properties, and origin of superoleophobicity for a model textured surface

Inspired by the superhydrophobic effect displayed in nature, we set out to mimic the interplay between the chemistry and physics in the lotus leaf to see if the same design principle can be applied to control wetting and adhesion between toners and inks on various printing surfaces. Since toners and inks are organic materials, superoleophobicity has become our design target. In this work, we report the design and fabrication of a model superoleophobic surface on silicon wafer. The model surface was created by photolithography, consisting of texture made of arrays of ～3 μm diameter pillars, ～7 μm in height with a center-to-center spacing of 6 μm. The surface was then made oleophobic with a fluorosilane coating, FOTS, synthesized by the molecular vapor deposition technique with tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane. Contact angle measurement shows that the surface exhibits super repellency toward water and oil (hexadecane) with a water and hexadecane contact angles at 156° and 158°, respectively. Since the sliding angles for both liquids are also very small (～10°), we conclude that the model surface is both superhydrophobic and superoleophobic. By comparing with the contact angle data of the bare silicon surfaces (both smooth and textured), we also conclude that the superoleophobicity is a result of both surface texturing and fluorination. Results from investigations of the effects of surface modification and pillar geometry indicate that both surface oleophobicity and pillar geometry are contributors to the superoleophobicity. More specifically, we found that superoleophobicity can only be attained on our model textured surface when the flat surface coating has a relatively high oleophobicity (i.e., with a hexadecane contact angle of >73°). SEM examination of the pillars with higher magnification reveals that the side wall in each pillar is not smooth; rather it consists of a ～300 nm wavy structure (due to the Bosch etching process) from top to bottom. Comparable textured surfaces with (a) smooth straight side wall pillars and (b) straight side wall pillars with a 500 nm re-entrant structure made of SiO(2) were fabricated and the surfaces were made oleophobic with FOTS analogously. Contact angle data indicate that only the textured surfaces with the re-entrant pillar structure are both superoleophobic and superhydrophobic. The result suggests that the wavy structure at the top of each pillar is the main geometrical contributor to the superoleophobic property observed in the model surface.     

Removal of Organic Pollutants from Water Using Superwetting Materials

The frequent occurrence of water pollution accidents and the leakage of organic pollutants have caused severe environmental and ecological crisis. It is thus highly imperative to find efficient materials to solve the problem. Inspired by the lotus leaf, superwetting materials are receiving increasing attention in the field of removal of organic pollutants from water. Various superwetting materials have been successfully generated and integrated into devices for removal of organic pollutants from water. On the basis of our previous work in the field, we summarized in this account the progress of removal of (1) floating and underwater insoluble, (2) emulsified insoluble, and (3) both insoluble and soluble organic pollutants from water using superwetting materials including superhydrophobic & superoleophilic materials, superhydrophilic & underwater superoleophobic materials, and materials with controllable wettability. The superwetting materials are in the forms of 2D porous materials, 3D porous materials and particles, etc. Finally, the current state and future challenges in this field are discussed. We hope this account could shed light on the design of novel superwetting materials for efficient removal of organic pollutants from water.     

基于特殊润湿性材料的油水分离

频繁发生的石油泄漏事故以及工业含油污水的违规排放不仅造成了巨大的经济损失,而且严重破坏了人类赖以生存的生态环境。为了净化被油污染的水域,研究者们近年来开始研究出了各种特殊润湿性(如超疏水或超疏油)的材料用于实现油水分离。超疏水和超疏油可以通过设计材料表面的微观几何形貌和化学分子组成来获得。通过各种微纳制备手段使材料表现出对油和水截然相反的极端润湿性,是这类材料实现油水分离的关键所在。本文首先阐述了实现油水分离的重要意义,并介绍了材料表面润湿性的相关理论基础。根据材料对水和油所表现出的不同超疏液性与超亲液性,对油水分离材料从以下三类分别介绍：(ⅰ)超疏水/超亲油材料,(ⅱ)超疏油/超亲水材料,(ⅲ)智能响应润湿性材料。对于每一类油水分离材料,本文概括了国际上近期相关的代表性研究工作,包括材料的制备方法和实现油水分离的原理和过程,以及这些材料的主要特点和应用。最后,针对基于特殊润湿性材料实现油水分离,探讨了该研究领域目前存在的主要问题和面临的挑战,并对该领域的应用前景进行了展望。     

Synthesis of perpendicular nanorod arrays with hierarchical architecture and water slipping superhydrophobic properties

The utilization of vertically aligned smooth gold nanorod arrays with and without nanoporous tip architectures as superhydrophobic surfaces is described. Nanoporous architecture was produced on the tips of nanorods by selectively dissolving less noble components from the alloy nanorods. The resulting nanoscopic dual-size roughness features enhanced the surface dewettability after surface modification with low-surface-energy materials such as long-chain normal alkanethiols and fluorinated organic compounds. The surface cleaning properties were also tested with a rolling water droplet.     

Fluoropolymer materials and architectures prepared by controlled radical polymerizations

This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition-fragmentation chain transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including multifunctional and macroinitiators), ligands and other reaction conditions as well as some kinetics and conversions are discussed. Numerous possibilities for preparation of a variety of different block copolymers where one or more blocks are fluorinated are devoted particular attention. The advantageous properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel electronics have been fabricated. In addition, the possible fluorination of various surfaces through surface initiation is highlighted. A final part deals with the use of fluorine containing initiators and macroinitiators, and the applications on the novel materials derived thereof.     

Super water- and oil-repellent surfaces on intrinsically hydrophilic and oleophilic porous silicon films

We demonstrate that porous Si films fabricated by a convenient gold-assisted electroless etching process, which possess a hierarchical porous structure consisting of micrometer-sized asperities superimposed onto a network of nanometer-sized pores, are able to induce a superhydrophobic phenomenon on an intrinsically hydrophilic hydrogen-terminated Si surface and a superoleophobic phenomenon on an intrinsically oleophilic self-assembled monolayer-coated Si surface. Through comparison with porous Si films consisting of vertically aligned straight pores, which are hydrophilic and oleophilic, we show that an overhang structure resulting from the hierarchical porous structure is essential to preventing water and oil from penetrating the texture of the films and inducing the observed macroscopic superhydrophobic and superoleophobic phenomena.     

Facile preparation of superhydrophobic and oleophobic surfaces via the combination of Cu(0)‐mediated reversible‐deactivation radical polymerization and click chemistry

The fabrication of novel hydrophobic, superhydrophobic, and oleophobic surfaces on glass using nanosilica particles modified with polymer brushes prepared via surface initiated Cu(0)‐mediated reversible‐deactivation radical polymerization was demonstrated. Monomers including n‐butyl acrylate, 2,2,2‐trifluoroethyl methacrylate, and 1,1,1,3,3,3‐hexafluoroisopropyl acrylate were used to synthesize a series of nanosilica–polymer organic/inorganic hybrid materials. Products were analyzed using infrared spectroscopy, thermogravimetric analysis, scanning and transmission electron microscopy. The coated nanosilica showed core–shell structures that contains polymer brushes up to 67 wt %. The application of these particles for modifying surface wettability was examined by covalently attaching them to glass via a recently developed one‐pot “grafting to” methodology using “thio‐bromo click” chemistry. Atomic force microscopy topographic images show up to 25 times increase in roughness of the coated glass compared to blank glass sample. Contact angle measurements showed that nanosilica coated with PBA and PTFEM produced hydrophobic glass surfaces, while a superhydrophobic and oleophobic surface was generated using nanosilica functionalized with PHFIPA. This novel methodology can produce superhydrophobic and oleophobic surfaces in an easy and fast way without the need for tedious and time‐consuming processes, such as layer‐by‐layer deposition, high temperature calcination, and fluorinated oil infusion. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018     

Electrospinning of a functional perfluorinated block copolymer as a powerful route for imparting superhydrophobicity and corrosion resistance to aluminum substrates

Superhydrophobic aluminum surfaces with excellent corrosion resistance were successfully prepared by electrospinning of a novel fluorinated diblock copolymer solution. Micro- and nanostructuration of the diblock copolymer coating was obtained by electrospinning which proved to be an easy and cheap electrospinning technology to fabricate superhydrophobic coating. The diblock copolymer is made of poly(heptadecafluorodecylacrylate-co-acrylic acid) (PFDA-co-AA) random copolymer as the first block and polyacrylonitrile (PAN) as the second one. The fluorinated block promotes hydrophobicity to the surface by reducing the surface tension, while its carboxylic acid functions anchor the polymer film onto the aluminum surface after annealing at 130 °C. The PAN block of this copolymer insures the stability of the structuration of the surface during annealing, thanks to the infusible character of PAN. It is also demonstrated that the so-formed superhydrophobic coating shows good adhesion to aluminum surfaces, resulting in excellent corrosion resistance.     

油水分离用天然材料表面化学研究进展

油水乳液和油水混合物的分离对解决工业含油废水以及原油泄漏造成的污染问题具有重要的意义。近年来应用于油水分离的超润湿材料引起了广泛的关注,并展现出良好的应用前景。本文综述了近年来利用超润湿性低成本、环保的天然材料通过过滤和吸附技术分离油水乳液和混合物的研究进展。对于每一种天然材料,如沙粒、木材、椰子壳等,介绍了代表性的研究工作,阐述了其制备过程、润湿特性以及对油水混合物或者油水乳液的分离效果,并讨论了利用超亲水/水下超疏油、超疏水/超亲油两种类型的材料分离不混溶的油水混合物、"水包油"型乳液和"油包水"型乳液等三类油水混合物的物理化学机理。最后,对该领域的挑战和未来的发展方向进行了展望。     

Synthesis and surface properties of novel fluorinated polyurethane base on F‐containing chain extender

A novel fluorinated chain extender, (1‐(ethyl(2‐hydroxyethyl)amino)‐3‐ ((3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl)oxy)propan‐2‐ol) (FPO), was synthesized and characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and elemental analysis. Poly (ether urethane)s containing various amounts of the chain extender with fluorinated side chains (FPUs) were prepared by isophorone diisocyanate (IPDI), polytetra‐methylene‐ether‐glycol (PTMG), 3‐aminopropyltriethoxysilane (KH‐550), and 1,4‐butandiol (BDO). Films of FPUs were investigated by water absorption, contact angle, pencil hardness, adhesive force, and thermal analysis. Coating FPUs on micro‐nano concave‐convex structure plate realizes superhydrophobic performance. Scanning electron microscope (SEM) and atomic force microscopy (AFM) demonstrated that there is a lot of irregular concave‐convex structure, which forms a typical air cushion model. X‐ray photoelectron spectroscopy (XPS) analysis showed that surface fluorine content is 165% more than that of film average fluorine content. The superhydrophobic plate with 10% or higher F‐containing FPUs coating is of outstanding chemical corrosion resistance, excellent solvent resistance, and wear resistance.     

New mesogen with thermotropic cubic phase: 3,4,5‐tris‐(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluorohexadecyloxy)benzoic acid

A new mesogen, 3,4,5‐tris(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluoro‐hexadecyloxy)benzoic acid, with a thermotropic cubic phase was synthesized. The phase behaviour of the fluorinated compound and its corresponding non‐fluorinated analogue was investigated by differential scanning calorimetry, polarizing optical microscopy, and synchrotron small‐angle X‐ray diffraction. The fluorinated compound, which contains three partially perfluorinated alkoxy moieties and one carboxylic acid group capable of forming hydrogen bonding, exhibits a very interesting sequence of isotropic, cubic and hexagonal columnar phases, whereas its non‐fluorinated compound does not have a liquid crystalline phase. The cubic phase exists over a wide temperature range (from ～200°C to ～30°C on cooling) and is hence amenable to various physical measurements and potential applications. The ability to self‐assemble molecules into ordered superstructure via both partially perfluorinated chains and hydrogen bonding provides new insight for the development of novel liquid crystalline materials.     

低黏附耐酸碱水相超疏油铜表面的制备

制备了一种新型的耐酸碱性的水相超疏油铜表面. 在水相中,油滴在其表面上的接触角高达162°,同时极易滚动,表明所得到的表面不但具有水相超疏油特性,同时还表现出较低的黏附性及较强的耐酸碱能力. 在不同pH值（2~12）的水溶液中,这种低黏附超疏油特性依然存在. 研究表明,该表面的水下超疏油及低黏附特性主要源于表面亲水性的化学组成及独特的微纳米等级结构之间的协同作用. 而较强的耐酸碱性则得益于铜材料自身较好的化学稳定性.     

氟代位置对苝酰亚胺聚集态结构和电子传输性能的影响

合成了三种新型的有机电子受体: N,N'-二(2-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D2MFPP)、N,N'-二(3-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D3MFPP)和N,N'-二(4-氟代苯基)-3,4,9,10-苝四羧基二酰亚胺(D4MFPP). 利用元素分析、傅立叶变换红外(FTIR)等方法表征了它们的分子结构, 用紫外-可见光吸收光谱(UV-Vis)、X射线衍射(XRD)和原子力显微镜(AFM)等手段研究了氟代位置对苝酰亚胺薄膜聚集态结构的影响, 发现氟代使苝酰亚胺的聚集态发生变化, 且不同位置的氟代对其影响也不一样. 除了分子结构的影响, 外场条件也会产生很大的作用. 通过制备场效应晶体管研究了其电子传输性能, 发现氟代后器件的空气稳定性有明显提高.