Multiscale roughness and stability of superhydrophobic biomimetic interfaces

The stability of a composite interface of roughness-induced superhydrophobic surfaces is studied. To have high contact angle and low contact angle hysteresis, superhydrophobic surfaces should be able to form a composite interface with air pockets in the valleys between asperities (pillars). However, the composite interface may be unstable and can be irreversibly transformed into a homogeneous interface. We formulate a stability criterion and analyze the stability of the composite interface for several typical roughness profiles. To resist destabilizing mechanisms, multiscale (hierarchical) roughness is required. Such multiscale roughness is found in natural and artificial superhydrophobic surfaces.     

含氟硅丙烯酸酯乳液超疏水膜中疏水基团的梯度分布与表面微观结构研究

利用含氟疏水基团的梯度分布,结合草莓形纳米SiO2粒子提供的双重粗糙表面,制备了具有类"荷叶效应"的超疏水涂膜,水接触角达(174.2±2)°,滞后角几乎接近0°.通过原子力显微镜、扫描电镜和水接触角的测试对膜表面形貌及疏水性能进行了表征;探讨了其表面微观结构与表面疏水性能的关系.草莓形复合粒子在膜表面的无规则排列赋予涂膜表面不同等级的粗糙度,使水滴与涂膜表面接触时能够形成高的空气捕捉率,这种微观结构与疏水基团的梯度分布相结合,赋予了含氟硅丙烯酸酯乳液涂膜表面超疏水性能.     

Contact line and contact angle dynamics in superhydrophobic channels

The dynamics of the wetting and movement of a three-phase contact line confined between two superhydrophobic surfaces were studied using a mean-field free-energy lattice Boltzmann model. Principle features of superhydrophobic surfaces, such as trapped vapor/air between rough microstructures, high contact angles, reduced contact angle hysteresis, and low resistance to fluid flow, were all observed. Movement of the three-phase contact line over a well-patterned superhydrophobic surface displays a periodic stick-jump-slip behavior, while the dynamic contact angle changes accordingly from maximum to minimum. Two regimes were found for the flow velocity as a function of surface roughness and can be related directly to the balance between driving force and flow resistance. This work provides a better understanding of dynamic wetting and fluid flow behaviors over superhydrophobic surfaces and hence could be useful in related applications.     

UV and thermally stable superhydrophobic coatings from sol-gel processing

A method for the preparation of inorganic superhydrophobic silica coatings using sol-gel processing with tetramethoxysilane and isobutyltrimethoxysilane as precursors is described. Incorporation of isobutyltrimethoxysilane into silica layers resulted in the existence of hydrophobic isobutyl surface groups, thereby generating surface hydrophobicity. When combined with the surface roughness that resulted from sol-gel processing, a superhydrophobic surface was achieved. This surface showed improved UV and thermal stability compared to superhydrophobic surfaces generated from polybutadiene by plasma etching. Under prolonged UV tests (ASTM D 4329), these surfaces gradually lost superhydrophobic character. However, when the as-prepared superhydrophobic surface was treated at 500 degrees C to remove the organic moieties and covered with a fluoroalkyl layer by a perfluorooctylsilane treatment, the surface regained superhydrophobicity. The UV and thermal stability of these surfaces was maintained upon exposure to temperatures up to 400 degrees C and UV testing times of 5500 h. Contact angles remained >160 degrees with contact angle hysteresis approximately 2 degrees.     

Effects of contact angle hysteresis on ice adhesion and growth on superhydrophobic surfaces under dynamic flow conditions

In this paper, the icephobic properties of superhydrophobic surfaces are investigated under dynamic flow conditions using a closed-loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared by coating aluminum and steel substrate plates with nano-structured hydrophobic particles. The superhydrophobic plates, along with uncoated controls, were exposed to a wind tunnel air flow of 12 m/s and ?7 °C with deviations of ±1 m/s and ±2.5 °C, respectively, containing micrometer-sized (～50 μm in diameter) water droplets. The ice formation and accretion were observed by CCD cameras. Results show that the superhydrophobic coatings significantly delay ice formation and accretion even under the dynamic flow condition of highly energetic impingement of accelerated supercooled water droplets. It is found that there is a time scale for this phenomenon (delay in ice formation) which has a clear correlation with contact angle hysteresis and the length scale of the surface roughness of the superhydrophobic surface samples, being the highest for the plate with the lowest contact angle hysteresis and finest surface roughness. The results suggest that the key for designing icephobic surfaces under the hydrodynamic pressure of impinging droplets is to retain a non-wetting superhydrophobic state with low contact angle hysteresis, rather than to only have a high apparent contact angle (conventionally referred to as a “static” contact angle).     

聚苯硫醚超疏水复合涂层的制备与性能

利用工业原料聚苯硫醚微粉和疏水性二氧化硅纳米粉末,采用喷涂法在瓷砖表面制备了疏水复合涂层.研究了热处理温度、组分配比对涂层表面形貌、粗糙度和接触角的影响,发现随着热处理温度升高,涂层表面粗糙度增大,随着疏水性二氧化硅含量的增加,由于表面聚集的疏水性二氧化硅增多,涂层疏水性增强,在热处理温度为280℃、疏水性二氧化硅与聚苯硫醚质量比为1∶1时,可获得超疏水涂层,涂层的接触角大于150°,滚落角小于4°,pH值为1～14的水溶液在其表面都具有很高的接触角.超疏水涂层具有良好的自清洁效果,并且经落沙法实验测定,超疏水涂层耐刮伤性能良好.     

Facile preparation of superhydrophobic coatings by sol-gel processes

Different organic/inorganic compositions and deposition methods were used to prepare superhydrophobic surfaces using metal alkoxides and the sol-gel process. Both surface roughness and composition had to be adjusted in order to obtain very high contact angles and low contact angle hysteresis as a necessary requirement for superhydrophobicity. Multilayer samples with a fluorinated organic-inorganic top layer showed water contact angles of about 157 degrees with low hysteresis (2 degrees ). Water drops rolled easily off their surface at a tilt angle as low as 4 degrees .     

Mimicking natural superhydrophobic surfaces and grasping the wetting process: a review on recent progress in preparing superhydrophobic surfaces

A typical superhydrophobic (ultrahydrophobic) surface can repel water droplets from wetting itself, and the contact angle of a water droplet resting on a superhydrophobic surface is greater than 150°, which means extremely low wettability is achievable on superhydrophobic surfaces. Many superhydrophobic surfaces (both manmade and natural) normally exhibit micro- or nanosized roughness as well as hierarchical structure, which somehow can influence the surface's water repellence. As the research into superhydrophobic surfaces goes deeper and wider, it is becoming more important to both academic fields and industrial applications. In this work, the most recent progress in preparing manmade superhydrophobic surfaces through a variety of methodologies, particularly within the past several years, and the fundamental theories of wetting phenomena related to superhydrophobic surfaces are reviewed. We also discuss the perspective of natural superhydrophobic surfaces utilized as mimicking models. The discussion focuses on how the superhydrophobic property is promoted on solid surfaces and emphasizes the effect of surface roughness and structure in particular. This review aims to enable researchers to perceive the inner principles of wetting phenomena and employ suitable methods for creation and modification of superhydrophobic surfaces.     

以砂纸为模板制作聚合物超疏水表面

报道了一种聚合物材料超疏水表面的简便制备方法. 以不同型号的金相砂纸为模板, 通过浇注成型或热压成型技术, 在聚合物表面形成不同粗糙度的结构. 接触角实验结果证明, 聚合物表面与水的接触角随着所用砂纸模板粗糙度的增加而加大, 其中粒度号为W7和W5砂纸制作的表面与水的接触角可超过150°, 显示出超疏水性质. 多种聚合物使用砂纸为模均可制备不同粗糙度及超疏水的表面, 本征接触角对复制表面浸润性的影响从Wenzel态到Cassie态而变小. 扫描电镜结果表明, 不规则形状的砂纸磨料颗粒构成了超疏水所需要的微纳米结构的模板.     

Fabrication of superhydrophobic surfaces of n-hexatriacontane

Superhydrophobic surfaces of n-hexatriacontane were fabricated in a single-step process. The low surface energy of n-hexatriacontane together with the randomly distributed micro- and nanoscale roughness features guarantees very large contact angles and a small roll-off angle for water drops. The advantage of n-hexatriacontane superhydrophobic surfaces is their stability in the sense that they are impervious to chemical reactions and retain their wetting characteristics over a long period of time, as confirmed by XPS analysis and contact angle measurements.     

Nano-scale superhydrophobicity: suppression of protein adsorption and promotion of flow-induced detachment

Wall adsorption is a common problem in microfluidic devices, particularly when proteins are used. Here we show how superhydrophobic surfaces can be used to reduce protein adsorption and to promote desorption. Hydrophobic surfaces, both smooth and having high surface roughness of varying length scales (to generate superhydrophobicity), were incubated in protein solution. The samples were then exposed to flow shear in a device designed to simulate a microfluidic environment. Results show that a similar amount of protein adsorbed onto smooth and nanometer-scale rough surfaces, although a greater amount was found to adsorb onto superhydrophobic surfaces with micrometer scale roughness. Exposure to flow shear removed a considerably larger proportion of adsorbed protein from the superhydrophobic surfaces than from the smooth ones, with almost all of the protein being removed from some nanoscale surfaces. This type of surface may therefore be useful in environments, such as microfluidics, where protein sticking is a problem and fluid flow is present. Possible mechanisms that explain the behaviour are discussed, including decreased contact between protein and surface and greater shear stress due to interfacial slip between the superhydrophobic surface and the liquid.     

Mimicking the lotus effect: influence of double roughness structures and slender pillars

Surface roughness is known to amplify hydrophobicity. The apparent contact angle of a drop on a rough surface is often modeled using either Wenzel's or Cassie's formulas. These formulas, along with an appropriate energy analysis, are critical in designing superhydrophobic substrates for applications in microscale devices. In this paper we propose that double (or multiple) roughness structures or slender pillars are appropriate surface geometries to develop "self-cleaning" surfaces. The key motivation behind the double structured roughness is to mimic the microstructure of superhydrophobic leaves (such as lotus). Theoretical analysis similar to that presented in the paper can be used to obtain optimal geometric parameters for the rough surface. The calculation procedure should result in surface geometries with excellent water repellent properties.     

Preparation of Cu-Coated Stainless Steel Surfaces for Superhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures with different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology. The resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

Preparation of Cu-Coated Stainless Steel Surfaces for Surperhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures having different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology, and the resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

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.     

一步阳极氧化法制备超亲水氧化铝

本文应用一步阳极氧化法在铝表面制作纳米粗糙结构的超亲水表面.考察控槽压、控电流及氧化时间对氧化铝表面超亲水性的影响.测试表明,控电流法更有利于制作超亲水表面,增大电流密度可缩短氧化时间,该法可制作稳定性好、机械强度高的超亲水氧化铝表面,富有潜在的应用价值.     

Cassie and Wenzel: were they really so wrong?

The properties of superhydrophobic surfaces are often understood by reference to the Cassie-Baxter and Wenzel equations. Recently, in a paper deliberately entitled to be provocative, it has been suggested that these equations are wrong; a suggestion said to be justified using experimental data. In this paper, we review the theoretical basis of the equations. We argue that these models are not so much wrong as have assumptions that define the limitations on their applicability and that with suitable generalization they can be used with surfaces possessing some types of spatially varying defect distributions. We discuss the relationship of the models to the previously published experiments and using minimum energy considerations review the derivations of the equations for surfaces with defect distributions. We argue that this means the roughness parameter and surface area fractions are quantities local to the droplet perimeter and that the published data can be interpreted within the models. We derive versions of the Cassie-Baxter and Wenzel equations involving roughness and Cassie-Baxter solid fraction functions local to the three-phase contact line on the assumption that the droplet retains an average axisymmetry shape. Moreover, we indicate that, for superhydrophobic surfaces, the definition of droplet perimeter does not necessarily coincide with the three-phase contact line. As a consequence, the three-phase contact lines within the contact perimeter beneath the droplet can be important in determining the observed contact angle on superhydrophobic surfaces.     

Fabrication and superhydrophobicity of fluorinated titanium dioxide nanocoatings

This study demonstrates the fabrication of a stable superhydrophobic surface with low contact angle hysteresis (CAH) using an arrangement of nanoscale TiO₂ spheres. The control of precursor quantity is selected as the key factor in determining surface roughness that significantly intensifies water contact angle (CA) of TiO₂ films. After surface fluorination treatment, the anatase-type crystalline surfaces exhibit good water repellency (CA 166.1°), low CAH (6°), and superhydrophobic stability (>60 min). Enhanced water repellency is attributed to the fact that the higher density of TiO₂ spheres results in more tortuous three-phase contact line, leading to the self-cleaning effect. Such a unique textured surface imparts many promising potentials for engineering and the development of optics devices with robust superhydrophobic materials.     

Superhydrophobicity on two-tier rough surfaces fabricated by controlled growth of aligned carbon nanotube arrays coated with fluorocarbon

Considerable effort has been expended on theoretical studies of superhydrophobic surfaces with two-tier (micro and nano) roughness, but experimental studies are few due to the difficulties in fabricating such surfaces in a controllable way. The objective of this work is to experimentally study the wetting and hydrophobicity of water droplets on two-tier rough surfaces for comparison with theoretical analyses. To compare wetting on micropatterned silicon surfaces with wetting on nanoscale roughness surfaces, two model systems are fabricated: carbon nanotube arrays on silicon wafers and carbon nanotube arrays on carbon nanotube films. All surfaces are coated with 20 nm thick fluorocarbon films to obtain low surface energies. The results show that the microstructural characteristics must be optimized to achieve stable superhydrophobicity on microscale rough surfaces. However, the presence of nanoscale roughness allows a much broader range of surface design criteria, decreases the contact angle hysteresis to less than 1 degrees , and establishes stable and robust superhydrophobicity, although nanoscale roughness could not increase the apparent contact angle significantly if the microscale roughness dominates.