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).     

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.     

Durable Lotus-effect surfaces with hierarchical structure using micro- and nanosized hydrophobic silica particles

Surfaces with a very high apparent water contact angle (CA) and low water contact angle hysteresis (CAH) exhibit many useful characteristics, among them extreme water repellency, low drag for fluid flow, and a self-cleaning effect. The leaf of the Lotus plant (Nelumbo nucifera) achieves these properties using a hierarchical structure with roughness on both the micro- and nanoscale. It is of great interest to create durable surfaces with the so-called "Lotus effect" for many important applications. In this study, hierarchically structured surfaces with Lotus-effect properties were fabricated using micro- and nanosized hydrophobic silica particles and a simple spray method. In addition, hierarchically structured surfaces were prepared by spraying a nanoparticulate coating over a micropatterned surface. To examine the similarities between surfaces using microparticles versus a uniform micropattern as the microstructure, CA and CAH were compared across a range of pitch values for the two types of microstructures. Wear experiments were performed using an atomic force microscope (AFM), a ball-on-flat tribometer, and a water jet apparatus to verify multiscale wear resistance. These surfaces have potential uses in engineering applications requiring Lotus-effect properties and high durability.     

Modification of the glass surface property in PDMS-glass hybrid microfluidic devices

This paper presents a simple method to change the hydrophilic nature of the glass surface in a poly(dimethylsiloxane) (PDMS)-glass hybrid microfluidic device to hydrophobic by an extra-heating step during the fabrication process. Glass substrates bonded to a native or oxygen plasma-treated PDMS chip having microchambers (12.5 mm diameter, 110 μm height) were heated at 200°C for 3 h, and then the hydrophobicity of the glass surfaces on the substrate was evaluated by measuring the contact angle of water. By the extra-heating process, the glass surfaces became hydrophobic, and its contact angle was around 109°, which is nearly the same as native PDMS surfaces. To demonstrate the usefulness of this surface modification method, a PDMS-glass hybrid microfluidic device equipped with microcapillary vent structures for pneumatic manipulation of droplets was fabricated. The feasibility of the microcapillary vent structures on the device with the hydrophobic glass surfaces are confirmed in practical use through leakage tests of the vent structures and liquid handling for the electrophoretic separation of DNA molecules.     

花生叶表面的高黏附超疏水特性研究及其仿生制备

花生是一种常见的豆科作物.与低黏附超疏水的荷叶不同,花生叶表面同时具有超疏水和高黏附特性.水滴在花生叶表面的接触角为151±2°,显示出超疏水特性.此外,水滴可以牢固地附着在花生叶表面,将花生叶翻转90°甚至180°,水滴均不会从表面滚落,显示了良好的黏附性(黏附力超过80μN).研究发现,花生叶表面呈现微纳米多级结构,丘陵状微米结构表面具有无规则排列的纳米结构.花生叶表面特殊的微纳米多尺度结构是其表面呈现高黏附超疏水特性的关键因素.结合实验数据,对花生叶表面特殊浸润性机理进行了简要阐述.受此启发,利用聚二甲基硅氧烷复形得到了与花生叶表面微结构类似的高黏附疏水表面.本文以期为仿生制备高黏附超疏水表面提供新思路.     

ICP刻蚀硅模板用于PDMS规则超疏水表面的制作

在ICP(inductively coupled plasma)刻蚀后的硅模板上复制聚二甲基硅氧烷(PDMS),经剥离得到含有一定尺寸的规则微柱阵列疏水表面.实验表明,当微柱高度较小时,微柱高度和边长对接触角有正影响,而间距则呈负影响;但如微柱高度较大,则高度对接触角的影响趋小,而边长呈负影响.间距对接触角的影响表现复杂.微柱间距6μm,边长14μm和高14μm微柱阵列的PDMS表面,静态接触角最大,约151°.     

Enhanced super-hydrophobic and switching behavior of ZnO nanostructured surfaces prepared by simple solution--immersion successive ionic layer adsorption and reaction process

A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows.     

Silver hierarchical bowl-like array: synthesis, superhydrophobicity, and optical properties

We present a facile synthetic route to a silver bowl-like array film with hierarchical structures on glass substrate using the colloidal monolayer as a template. In these special hierarchical structures, microstructures were provided by a colloidal template of polystyrene latex spheres and nanostructures resulting from the thermal decomposition of silver acetate. These structures were chemically modified with 1-hexadecanethiol, and a corresponding self-assembled monolayer (SAM) was formed on their surfaces. Due to the lotus leaf-like morphology with hierarchical micro/nanostructures, the film displayed an extraordinary superhydrophobicity after chemical modification. Water contact angle and sliding angle were 169 degrees and 3 degrees (the weight of water droplets: 3 mg), respectively. Additionally, its optical property has also been investigated. This structure could be used in microfluidic devices, optical devices, and biological science.     

Dynamic wetting and spreading characteristics of a liquid droplet impinging on hydrophobic textured surfaces

We report on the wetting dynamics of a 4.3 μL deionized (DI) water droplet impinging on microtextured aluminum (Al 6061) surfaces, including microhole arrays (hole diameter 125 μm and hole depth 125 μm) fabricated using a conventional microcomputer numerically controlled (μ-CNC) milling machine. This study examines the influence of the texture area fraction ?(s) and drop impact velocity on the spreading characteristics from the measurement of the apparent equilibrium contact angle, dynamic contact angle, and maximum spreading diameter. We found that for textured surfaces the measured apparent contact angle (CA) takes on values of up to 125.83°, compared to a CA of approximately 80.59° for a nontextured bare surface, and that the spreading factor decreases with the increased texture area fraction because of increased hydrophobicity, partial penetration of the liquid, and viscous dissipation. In particular, on the basis of the model of Ukiwe and Kwok (Ukiwe, C.; Kwok, D. Y. Langmuir 2005, 21, 666), we suggest a modified equation for predicting the maximum spreading factor by considering various texturing effects and wetting states. Compared with predictions by using earlier published models, the present model shows better agreement with experimental measurements of the maximum spreading factor.     

Self-assembled biomimetic superhydrophobic CaCO3 coating inspired from fouling mineralization in geothermal water

Inspired from fouling self-mineralization in geothermal water, a novel biomimetic cactuslike CaCO(3) coating with superhydrophobic features is reported in this letter. The structure, morphologies, and phases of the CaCO(3) coating were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and infrared spectrophotometry. After prenucleation treatment, a continuous cactuslike CaCO(3) coating with hierarchical nano- and microstructures was self-assembled on stainless steel surfaces after immersion in simulated geothermal water at 50 °C for 48 h. After being modified with a low-surface-energy monolayer of sodium stearate, the as-prepared coating exhibited superhydrophobic properties with a water contact angle of 158.9° and a sliding angle of 2°. Therefore, this work might open up a new application field of geothermal resources and provide insight into designing multidimensional structures with functional applications, including superhydrophobic surfaces.     

Directional self-cleaning superoleophobic surface

In this work, we report the creation of a grooved surface comprising 3 μm grooves (height ～4 μm) separated by 3 μm from each other on a silicon wafer by photolithography. The grooved surface was then modified chemically with a fluorosilane layer (FOTS). The surface property was studied by both static and dynamic contact angle measurements using water, hexadecane, and a polyethylene wax ink as the probing liquids. Results show that the grooved surface is both superhydrophobic and superoleophobic. Its observed contact angles agree well with the calculated Cassie-Baxter angles. More importantly, we are able to make a replica of the composite wax ink-air interface and study it by SEM. Microscopy results not only show that the droplet of the wax ink "sits" on air in the composite interface but also further reveal that the ink drop actually pins underneath the re-entrant structure in the side wall of the grooved structure. Contact angle measurement results indicate that wetting on the grooved surface is anisotropic. Although liquid drops are found to have lower static and advancing contact angles in the parallel direction, the drops are found to be more mobile, showing smaller hysteresis and lower sliding angles (as compared to the FOTS wafer surface and a comparable 3-μm-diameter pillar array FOTS surface). The enhanced mobility is attributable to the lowering of the resistance against an advancing liquid because 50% of the advancing area is made of a solid strip where the liquid likes to wet. This also implies that the contact line for advancing is no longer smooth but rather is ragged, having the solid strip area leading the wetting and the air strip area trailing behind. This interpretation is supported by imaging the geometry of the contact lines using molten ink drops recovered from the sliding angle experiments in both the parallel and orthogonal directions. Because the grooved surface is mechanically stronger against mechanical abrasion, the self-cleaning effect exhibited in the parallel direction suggests that groove texturing is a viable approach to create mechanically robust, self-cleaning, superoleophobic surfaces.     

水下超疏油仿生特殊粘附界面材料的研究进展

水下超疏油表面由于在防污材料、微流控技术、生物粘附等方面具有广泛的应用前景,已经引起人们的普遍关注。本文简单介绍了浸润性在液相体系的相关概念及基础理论,综述了自然界中的水下超疏油低粘附生物体典型实例以及水下超疏油仿生特殊粘附界面材料的仿生制备和智能调控,并对水下超疏油仿生界面材料的发展进行了展望。     

仿生水下超疏油表面

水下超疏油表面是指在油/水/固三相体系中,对油的接触角大于150°的固体表面.从鱼体表面和荷叶下表面2种具有水下超疏油性质的生物体系出发,讨论了影响水下超疏油性质的因素,并据此提出了仿生水下超疏油表面的设计方法.通过介绍目前典型的人造水下超疏油表面的制备手段和研究进展,概括了水下超疏油体系的发展现状.对浸润性和黏附性响应性可控的智能水下超疏油体系以及水下超疏油体系在液滴操控、抗生物黏附和油水分离等领域的应用进行了简要介绍.最后对仿生水下超疏油体系目前研究存在的问题及挑战进行了总结,在此基础上展望了该领域未来的发展方向.     

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.     

A vertical microfluidic probe

Performing localized chemical events on surfaces is critical for numerous applications. We earlier invented the microfluidic probe (MFP), which circumvented the need to process samples in closed microchannels by hydrodynamically confining liquids that performed chemistries on surfaces (Juncker et al. Nat. Mater. 2005, 4, 622-628). Here we present a new and versatile probe, the vertical MFP (vMFP), which operates in the scanning mode while overcoming earlier challenges that limited the practical implementation of the MFP technology. The key component of the vMFP is the head, a microfluidic device (～1 cm(2) in area) consisting of glass and Si and having microfluidic features fabricated in-plane in the Si layer. The base configuration of the head has two micrometer-size channels that inject/aspirate liquids and terminate at the apex which is ～1 mm(2). In scanning mode, the head is oriented vertically with the apex parallel to the surface with typical spacing of 1-30 μm. Such length scales and using flow rates from nanoliters/second to microliters/second allow chemical events to be performed on surfaces with tens of picoliter quantities of reagents. Before scanning, the head is clipped on a holder for leak-free, low dead volume interface assembly, providing a simple world-to-chip interface. Surfaces are scanned by mounting the holder on a computer-controlled stage having ～0.1 μm resolution in positioning. We present detailed steps to fabricate vMFP heads having channels with dimensions from 1 μm × 1 μm to 50 μm × 50 μm for liquid localization over areas of 10-10,000 μm(2). Additionally, advanced design strategies are described to achieve high yield in fabrication and to support a broad range of applications. These include particulate filters, redundant aperture architectures, inclined flow-paths that service apertures, and multiple channels to enable symmetric flow confinement. We also present a method to characterize flow confinement and estimate the distance between the head and the surface by monitoring the evolution of a solution of fluorescently labeled antibody on an activated glass surface. This flow characterization reveals regimes of operation suitable for different surface topographies. We further integrate the dispensing of immersion liquid to the vMFP head for processing surfaces for extended periods of time (～60 min). The versatility of the vMFP is exemplified by patterning fluorescently labeled proteins, inactivation of cells using sodium hypochlorite, and staining living NIH fibroblasts with Cellomics. These applications are enabled by the compact design of the head, which provides easy access to the surface, simplifies alignment, and enables processing surfaces having dimensions from the micrometer to the centimeter scale and with large topographical variations. We therefore believe that ease-of-operation, reconfigurability, and conservative use of chemicals by the vMFP will lead to its widespread use by microtechnologists and the chemical and biomedical communities.     

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.     

Nonswellable hydrogels with robust micro/nano-structures and durable superoleophobic surfaces under seawater

Hydrogels, composed mainly of water trapped in three dimensional cross-linked polymer networks, have been widely utilized to construct underwater superoleophobic surfaces. However, the swelling nature and instability of hydrogels under complex marine environment will weaken their underwater superoleophobicity. Herein, we synthesize structured poly(2-hydroxyethylmethacrylate)(PHEMA) hydrogels by using sandpaper as templates. The robust non-swelling of PHEMA hydrogel ensures that micro/nano-structures on the surface of PHEMA hydrogels can be well maintained. Moreover, when roughness Ra of about 3~4 μm, the surface has superior oil-repellency. Additionally, even after immersing in seawater for one-month, their breaking strength and toughness can be well kept. The non-swellable hydrogels with long-term stable under seawater superoleophobicity will promote the development of robust superoleophobic materials in marine antifouling coatings,biomedical devices and oil/water separation.     

Preparation of superhydrophobic Fe2O3 nanorod films with the tunable water adhesion

We describe a simple and inexpensive method to prepare α-Fe(2)O(3) nanorods films on glass slides fabricated via a simple hydrothermal procedure at 120 °C. Such films exhibit a hierarchical microtexture, and after the surface modification, they show extraordinary superhydrophobicity and the controllable water adhesion. Such superhydrophobic surfaces of the ferric oxides imply wide industrial applications.     

A nonlithographic top-down electrochemical approach for creating hierarchical (micro-nano) superhydrophobic silicon surfaces

Superhydrophobic surfaces are biomimetic structures with potential applications in several key technological areas. In the past decade, several top-down and bottom-up fabrication methods have been developed to create such surfaces. These typically combine a hierarchical structure and low surface energy coatings to increase the contact angle and decrease the rolling angles. Silicon-based superhydrophobic surfaces are particularly attractive since they can be integrated with active electronics in order to protect them from the detrimental effects of environmental water and moisture. In this work, we introduce a simple and inexpensive process incorporating electrochemical surface modification (to create a fractal shape micro-nano topography) in combination with a final wet etching step to fabricate a superhydrophobic silicon surface with a contact angle of 160 degrees and a sliding angle of less than 1 degree.     

Flexible Broadband Light Absorbers with a Superhydrophobic Surface Fabricated by Ultraviolet-assisted Nanoimprint Lithography

We present a simple approach to fabricate a kind of composite films with a superhydrophobic and broadband light absorbing surface by ultraviolet-assisted nanoimprinting over a gradiently deposited composite matrix. The wettability and optical property of the resultant surfaces are tunable by the deposition time before polymerization(T_s) and mold's topography. Mechanically robust and elastomeric films exhibiting high sunlight absorptivity up to 98.13% and contact angle of their surfaces up to 150° are prepared under optimized conditions, as using a mold with a small pattern size(hexagonal periodic mold with cylinder diameter of ca. 37 μm) under T_s=10 min for imprinting the crosslinked poly[di(ethylene glycol) ethyl ether acrylate] and poly(isobornyl acrylate) in the presence of polypyrrole(PPy) nanoparticles. Such dual functions are found related to the hierarchical architecture of the surface, arising from the synergetic effects of the periodical patterned polymer substrate and spontaneously assembled PPy microstructures on the patterns. The current strategy based on the combination of ultraviolet-assisted nanoimprint lithography and hierarchical assembly of gradiently deposited black nano-fillers offers a new insight into the design of robust superhydrophobic and black surfaces, which is helpful to deepen our understanding of the relationship between liquid/light manipulation and micro/nanostructured surfaces.