Facile creation of hierarchical PDMS microstructures with extreme underwater superoleophobicity for anti-oil application in microfluidic channels

Composition modification and surface microstructures have been widely utilized in interface science to improve the surface performance. In this paper, we observed a significant improvement of oil contact angle (CA) from 66 ± 2° to 120 ± 4° by introducing a radical silanol group on a flat PDMS surface through oxygen plasma pretreatment. By combining surface microstructures and plasma modification, we produced three kinds of superoleophobic surfaces: 20 μm pitch micropillar arrays, 2.5 μm pitch micropillar arrays and gecko foot-like hierarchical microstructures. Among them, the hierarchical surface with high surface roughness showed extreme underwater superoleophobicity, which featured ultrahigh CA (175 ± 3°) and ultrasmall sliding angle (<1°). Quantitative measurements demonstrated that these superoleophobic surfaces exhibited distinct adhesive behaviors, by which they were interpreted as Wenzel's, Cassie's and the Lotus state, respectively. A microfluidic channel with superoleophobic microstructures was further created by novel curve-assisted imprint lithography, and the characterization based on anti-oil contamination applications was carried out and discussed. We believe that the superoleophobic surfaces will power broad applications in oil microdroplet transportation, anti-oil channels and droplet microfluidic systems.     

Roughness assessment and wetting behavior of fluorocarbon surfaces

The wetting behavior of fluorocarbon materials has been studied with the aim of assessing the influence of the surface chemical composition and surface roughness on the water advancing and receding contact angles. Diamond like carbon and two fluorocarbon materials with different fluorine content have been prepared by plasma enhanced chemical vapor deposition and characterized by X-ray photoemission, Raman and FT-IR spectroscopies. Very rough surfaces have been obtained by deposition of thin films of these materials on polymer substrates previously subjected to plasma etching to increase their roughness. A direct correlation has been found between roughness and water contact angles while a superhydrophobic behavior (i.e., water contact angles higher than 150° and relatively low adhesion energy) was found for the films with the highest fluorine content deposited on very rough substrates. A critical evaluation of the methods currently used to assess the roughness of these surfaces by atomic force microscopy (AFM) has evidenced that calculated RMS roughness values and actual surface areas are quite dependent on both the scale of observation and image resolution. A critical discussion is carried out about the application of the Wenzel model to account for the wetting behavior of this type of surfaces.     

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。     

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.     

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.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

Creation of low hysteresis superhydrophobic paper by deposition of hydrophilic diamond-like carbon films

The creation of low hysteresis superhydrophobic paper is reported using a combination of oxygen plasma etching and plasma deposition of an 80 nm non-fluorinated, hydrophilic diamond-like carbon (DLC) coating. The DLC has an equilibrium (flat surface) contact angle (θ _e ) of 68.2° ± 1.5°, which is well below the 90° contact angle that is typically believed to be a prerequisite for superhydrophobicity. Coating of paper substrates with the DLC film yields an advancing contact angle of 124.3° ± 4.1°, but the surface remains highly adhesive, with a receding contact angle <10°. After 60 min of plasma etching and DLC coating, a low hysteresis, superhydrophobic surface is formed with an advancing contact angle of 162.0° ± 6.3° and hysteresis of 8.7° ± 1.9°. To understand the increase in contact angle and decrease in hysteresis, atomic force microscopy and optical profilometry studies were performed. The data demonstrates that while little additional nanoscale roughness is imparted beyond the first 5 min of etching, the roughness at the microscale continually increases. The hierarchical structure provides the appropriate roughness to create low hysteresis superhydrophobic paper from a hydrophilic coating.     

Superhydrophobic silicon surfaces with micro-nano hierarchical structures via deep reactive ion etching and galvanic etching

An effective fabrication method combining deep reactive ion etching and galvanic etching for silicon micro-nano hierarchical structures is presented in this paper. The method can partially control the morphology of the nanostructures and enables us to investigate the effects of geometry changes on the properties of the surfaces. The forming mechanism of silicon nanostructures based on silver nanoparticle galvanic etching was illustrated and the effects of process parameters on the surface morphology were thoroughly discussed. It is found that process parameters have more impact on the height of silicon nanostructure than its diameter. Contact angle measurement and tilting/dropping test results show that as-prepared silicon surfaces with hierarchical structures were superhydrophobic. What's more, two-scale model composed of micropillar arrays and nanopillar arrays was proposed to study the wettability of the surface with hierarchical structures. Wettability analysis results indicate that the superhydrophobic surface may demonstrate a hybrid state at which water sits on nanoscale pillars and immerses into microscale grooves partially.     

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.     

Extremely superhydrophobic surfaces with micro- and nanostructures fabricated by copper catalytic etching

We demonstrate a simple method for the fabrication of rough silicon surfaces with micro- and nanostructures, which exhibited superhydrophobic behaviors. Hierarchically rough silicon surfaces were prepared by copper (Cu)-assisted chemical etching process where Cu nanoparticles having particle size of 10-30 nm were deposited on silicon surface, depending on the period of time of electroless Cu plating. Surface roughness was controlled by both the size of Cu nanoparticles and etching conditions. As-synthesized rough silicon surfaces showed water contact angles ranging from 93° to 149°. Moreover, the hierarchically rough silicon surfaces were chemically modified by spin-coating of a thin layer of Teflon precursor with low surface energy. And thus it exhibited nonsticky and enhanced hydrophobic properties with extremely high contact angle of nearly 180°.     

Fabrication of "roll-off" and "sticky" superhydrophobic cellulose surfaces via plasma processing

Most of the artificial superhydrophobic surfaces that have been fabricated to date are not biodegradable, renewable, or mechanically flexible and are often expensive, which limits their potential applications. In contrast, cellulose, a biodegradable, renewable, flexible, inexpensive, biopolymer which is abundantly present in nature, satisfies all the above requirements, but it is not superhydrophobic. Superhydrophobicity on cellulose paper was obtained by domain-selective etching of amorphous portions of the cellulose in an oxygen plasma and subsequently coating the etched surface with a thin fluorocarbon film deposited via plasma-enhanced chemical vapor deposition using pentafluoroethane as a precursor. Variation of plasma treatment yielded two types of superhydrophobicity : "roll-off" (contact angle (CA), 166.7 degrees +/- 0.9 degrees ; CA hysteresis, 3.4 degrees +/- 0.1 degrees ) and "sticky" (CA, 144.8 degrees +/- 5.7 degrees ; CA hysteresis, 79.1 degrees +/- 15.8 degrees ) near superhydrophobicity. The nanometer scale roughness obtained by delineating the internal roughness of each fiber and the micrometer scale roughness which is inherent to a cellulose paper surface are robust when compared to roughened structures created by traditional polymer grafting, nanoparticle deposition, or other artificial means.     

超声刻蚀法构建分级结构的超疏水表面

在湿法刻蚀和超声空化的基础上, 采用超声刻蚀法制备了具有微纳米分级结构的超疏水表面. 以等体积比的硝酸/乙醇(体积分数为4%)和双氧水(质量分数为30%)的混合溶液作为刻蚀剂, 在室温下对60Si2Mn钢、 60^#钢、 T10钢、 Cr06钢、 65Mn钢和硅钢表面超声刻蚀2~10 min, 构建出多种形貌的微纳米分级结构. 上述表面经氟硅烷修饰后具有超疏水性, 水的表观接触角高达157.0°, 155.8°, 157.4°, 154.9°, 157.6°和156.8°, 滚动角分别为6.5°, 19.2°, 6.1°, 7.8°, 6.7°和7.2°. 与常规刻蚀方法相比, 超声刻蚀的化学刻蚀作用因与空化作用耦合而得到强化和改变, 从而在钢表面构建出分级结构. 由于材料表面微结构形貌和固/液界面接触状态不同, 制得的超疏水表面表现出的润湿行为也不同. 超声刻蚀法简单易行, 成本低廉, 适用于其它金属表面构建微纳米分级结构和超疏水表面.     

Polystyrene‐grafted Al surface with excellent superhydrophobicity and corrosion resistance

A superhydrophobic Al surface was successfully fabricated by a facile and environmentally friendly method as the boiling water treatment and 3‐glycidoxypropyl trimethoxysilane (GPS) as well as carboxyl‐terminated polystyrene (PS‐COOH) modification. The fabrication procedure, morphology, composition, and corrosion resistance of the superhydrophobic Al surface were investigated. Results show that the treatment in the boiling water endows the Al surface with the porous and roughened structure, while the modification with GPS as well as PS‐COOH grafts the long PS chains onto the micro‐scale and nano‐scale hierarchical structure. Consequently, a superhydrophobic Al surface with a contact angle of 153.6° and a rolling angle of 3° is obtained. Additionally, a vast majority of surface area is covered by the air in the solid–liquid contact area for the superhydrophobic Al surface, and which can prevent the corrosive ions entering into the Al surface. As a result, the corrosion resistance is improved greatly. Copyright © 2015 John Wiley & Sons, Ltd.     

低能量链端对聚苯乙烯薄膜铺展和润湿行为的影响

通过低能量功能端基的表面富集作用,研究了聚苯乙烯（ＰＳ）薄膜在聚甲基丙烯酸甲酯（ＰＭＭＡ）表面上的铺展和润湿动力学．用光学显微镜跟踪了ＰＳ薄膜的润湿行为,并对高分子熔体膜中非连续部分尺寸的增大速率进行了测定．分别用ＸＰＳ和ＡＦＭ对ＰＳ薄膜的表面组成和ＰＳ液滴的平衡接触角进行了测定．发现具有低表面能的氟碳端基在薄膜表面富集使ＰＳ薄膜的表面张力下降,并使ＰＳ液滴在ＰＭＭＡ表面上的平衡接触角减小,从而使高分子熔体膜中非连续部分尺寸的增长速率下降,得到了与液液界面铺展和润湿理论一致的实验结果．     

Multifunctional polymethylsilsesquioxane (PMSQ) surfaces prepared by electrospinning at the sol-gel transition: superhydrophobicity, excellent solvent resistance, thermal stability and enhanced sound absorption property

Multifunctional superhydrophobic polymethylsilsesquioxane (PMSQ) surfaces with excellent solvent resistance, thermal stability and enhanced sound absorption property were manufactured by electrospinning. The surfaces with various hierarchical morphologies and hydrophobicity were obtained by electrospinning at the different stages of sol-gel transition of PMSQ prepolymer solution. At the stage with a proper viscosity the superhydrophobic PMSQ surface with a contact angle as high as 151° and a sliding angle as low as 8° was prepared. Due to the excellent thermal stability and solvent resistance properties of the cured PMSQ, the resultant surfaces remain superhydrophobicity after thermal treatment at 300 °C and immersion into many solvents. Additionally, an enhanced acoustical performance and ultra water repellency were obtained simultaneously when the traditional acoustical sponge was decorated with the electrospun PMSQ superhydrophobic surface. The robust superhydrophobic PMSQ surfaces may promise practical applications in many fields.     

特殊浸润性表面的液滴凝结

以铝片为基底, 经电化学腐蚀和沸水处理制备了多级微纳米结构; 通过气相沉积和涂油分别制备了超疏水表面、 疏水超润滑(slippery)表面和亲水slippery表面; 探究了表面不同的特殊浸润性(超亲水、 超疏水、 疏水slippery和亲水slippery)对液滴凝结的影响. 结果表明, 超亲水表面的液滴凝结属于膜状冷凝, 超疏水表面和slippery表面的液滴凝结均属于滴状冷凝. 超疏水表面液滴合并时, 合并的液滴会不定向弹离表面. 疏水slippery表面和亲水slippery表面由于表面浸润性的不同导致液滴成核密度和液滴合并的差异, 亲水slippery表面凝结液滴的最大体积远大于疏水slippery表面凝结液滴的最大体积. 4种表面的雾气收集效率由大到小依次为亲水slippery表面>疏水slippery表面>超亲水表面>超疏水表面.     

Design and fabrication of a superhydrophobic glass surface with micro-network of nanopillars

The wetting property of a superhydrophobic glass surface with a micro-network of nanopillars fabricated from colloidal lithography and plasma etching is investigated in this paper. The micro-network distribution of nanospheres can be modulated by diluting the nanosphere concentration and controlling the spin rate. The micro-network of nanospheres spun on the glass surface serves as a mask for nanopillars during the plasma etching process. After the fabrication, the nano-structured surface is treated with fluoroalkylsilane self-assembled monolayers to obtain superhydrophobicity. Among several spin rates, the minimum colloidal network area density from a 100 nm polystyrene nanosphere solution diluted to 0.026% was found at a spin rate of 4000 rpm. The sample with the lowest network area density shows a good quality of superhydrophobicity, having the highest water contact angle and the lowest sliding angle among samples with other network area densities. In particular, samples with a micro-network of pillars also showed mechanical robustness against finger rubbing. To assess the superhydrophobic behavior in-depth, a size-dependent contact angle equation is proposed for use with a high contact angle (>135°) and with a Bo (Bond number) ? 1. Furmidge's sliding angle equation is also modified; it is derived considering a static contact angle to simplify the prediction of the sliding angle. The contact and sliding angle measurements from samples with a micro-network of nanopillars show good agreement with the proposed equations.     

One-step fabrication of nanostructured Ni film with lotus effect from deep eutectic solvent

We report a procedure to fabricate nanostructured Ni films via programmed electrochemical deposition from a choline-chloride-based ionic liquid at a high temperature of 90 °C. Three electrodeposition modes using constant voltage, pulse voltage, and reverse pulse voltage produce a variety of nanostructured Ni films with micro/nanobinary surface architectures, such as nanosheets, aligned nanostrips, and hierarchical flowers. The nanostructured Ni films possess face-centered cubic crystal structure. Amazingly, it is found that the electrodeposited Ni films deliver the superhydrophobic surfaces without any further modifications by low surface-energy materials, which might be attributed to the vigorous micro/nanobinary architectures and the surface chemical composition. The electrochemical measurements reveal that the superhydrophobic Ni film exhibit an obvious passivation phenomenon, which could provide enhanced corrosion resistance for the substrate in the aqueous solutions.     

Amphiphilic Janus Gold Nanoparticles Prepared by Interface‐Directed Self‐Assembly: Synthesis and Self‐Assembly

Materials with Janus structures are attractive for wide applications in materials science. Although extensive efforts in the synthesis of Janus particles have been reported, the synthesis of sub‐10 nm Janus nanoparticles is still challenging. Herein, the synthesis of Janus gold nanoparticles (AuNPs) based on interface‐directed self‐assembly is reported. Polystyrene (PS) colloidal particles with AuNPs on the surface were prepared by interface‐directed self‐assembly, and the colloidal particles were used as templates for the synthesis of Janus AuNPs. To prepare colloidal particles, thiol‐terminated polystyrene (PS‐SH) was dissolved in toluene and citrate‐stabilized AuNPs were dispersed in aqueous solution. Upon mixing the two solutions, PS‐SH chains were grafted to the surface of AuNPs and amphiphilic AuNPs were formed at the liquid–liquid interface. PS colloidal particles decorated with AuNPs on the surfaces were prepared by adding the emulsion to excess methanol. On the surface, AuNPs were partially embedded in the colloidal particles. The outer regions of the AuNPs were exposed to the solution and were functionalized through the grafting of atom‐transfer radical polymerization (ATRP) initiator. Poly[2‐(dimethamino)ethyl methacrylate] (PDMAEMA) on AuNPs were prepared by surface‐initiated ATRP. After centrifugation and dissolving the colloidal particles in tetrahydrofuran (THF), Janus AuNPs with PS and PDMAEMA on two hemispheres were obtained. In acidic pH, Janus AuNPs are amphiphilic and are able to emulsify oil droplets in water; in basic pH, the Janus AuNPs are hydrophobic. In mixtures of THF/methanol at a volume ratio of 1:5, the Janus AuNPs self‐assemble into bilayer structures with collapsed PS in the interiors and solvated PDMAEMA at the exteriors of the structures.     

Facile Electrochemical Method for the Fabrication of Stable Corrosion-Resistant Superhydrophobic Surfaces on Zr-Based Bulk Metallic Glasses

Both surface microstructure and low surface energy modification play a vital role in the preparation of superhydrophobic surfaces. In this study, a safe and simple electrochemical method was developed to fabricate superhydrophobic surfaces of Zr-based metallic glasses with high corrosion resistance. First, micro–nano composite structures were generated on the surface of Zr-based metallic glasses by electrochemical etching in NaCl solution. Next, stearic acid was used to decrease surface energy. The effects of electrochemical etching time on surface morphology and wettability were also investigated through scanning electron microscopy and contact angle measurements. Furthermore, the influence of micro–nano composite structures and roughness on the wettability of Zr-based metallic glasses was analysed on the basis of the Cassie–Baxter model. The water contact angle of the surface was 154.3° ± 2.2°, and the sliding angle was <5°, indicating good superhydrophobicity. Moreover, the potentiodynamic polarisation test and electrochemical impedance spectroscopy suggested excellent corrosion resistance performance, and the inhibition efficiency of the superhydrophobic surface reached 99.6%. Finally, the prepared superhydrophobic surface revealed excellent temperature-resistant and self-cleaning properties.