Hydrophobic properties of a wavy rough substrate

The wetting/non-wetting properties of a liquid drop in contact with a chemically hydrophobic rough surface (thermodynamic contact angle e>/2) are studied for the case of an extremely idealized rough profile: the liquid drop is considered to lie on a simple sinusoidal profile. Depending on surface geometry and pressure values, it is found that the Cassie and Wenzel states can coexist. But if the amplitude h of the substrate is sufficiently large the only possible stable state is the Cassie one, whereas if h is below a certain critical value hcr a transition to the Wenzel state occurs. Since in many potential applications of such super-hydrophobic surfaces, liquid drops often collide with the substrate (e.g. vehicle windscreens), in the paper the critical drop pressure pW is calculated at which the Cassie state is no longer stable and the liquid jumps into full contact with the substrate (Wenzel state). By analyzing the asymptotic behavior of the systems in the limiting case of a large substrate corrugation, a simple criterion is also proposed to calculate the minimum height asperity h necessary to prevent the Wenzel state from being formed, to preserve the super-hydrophobic properties of the substrate, and, hence, to design a robust super-hydrophobic surface.     

亲水性微观粗糙表面润湿状态转变性能研究

以亲水性微观粗糙表面上不同几何形貌及分布的微柱阵列为对象, 讨论了液滴在亲水性粗糙表面上的润湿过程以及润湿状态的转变阶段. 从能量角度分别考察了微观粗糙结构几何形貌及分布、微柱几何参数、固体表面亲水性、接触角滞后作用等因素对液滴润湿状态转变的影响规律. 研究发现: 在亲水粗糙表面, 正方形微柱呈正六边形阵列分布时, 液滴更容易形成稳定的Cassie状态, 或者液滴仅发生Cassie状态向中间浸润状态的转变; 与此同时, 减小微柱间距、增大方柱宽度或圆柱直径、增大微柱高度、增强固体表面的亲水性将有利于液滴处于稳定的Cassie状态, 或阻止润湿状态向伪-Wenzel或Wenzel状态转变; 然而, 当液滴处于Cassie状态时, 较小的固-液界面面积分数或减弱固体表面亲水性能均有利于增大液滴的表观接触角, 因此在亲水表面设计粗糙结构时应综合考虑润湿状态稳定性和较大表观接触角两方面因素; 此外, 接触角滞后作用对于液滴状态的稳定性以及疏水性能的实现具有相反作用的影响. 研究结果为液滴在亲水表面获得稳定Cassie状态的粗糙结构设计方法提供了理论依据. 关键词： 亲水表面 微观粗糙结构 表面自由能 润湿状态转变     

On a moving liquid film and its instability on textured surfaces

Recently, two regimes of viscous friction on textured surfaces were proposed in the context of penetration of liquid film into the texture (EPL 79, 56005 (2007)): the Poiseuille and Stokes regimes. With this idea on viscous friction, we theoretically discuss instabilities on a liquid film on textured surfaces when the film is forced to move with external forces. When a film recedes due to a pressure drop, we find scaling laws for instabilities to be checked in future experiments. When a circular film expands due to centrifugal force we find that the expanding film is stable against rim fluctuations (within the linear stability analysis) with its radius determined by a simple equation. Our discussion sheds light on the curvature of the front of the moving liquid film on textured surfaces and how the film thickness is kept fixed to the texture height on textured surfaces, aspects which have not been discussed in previous studies.     

Optimization of the surface texture for silicon carbide sliding in water

Surface texturing has been recognized as an effective means to improve the tribological performances of sliding surfaces. Usually, generation additional hydrodynamic pressure to increase the load carrying capacity is regarded as the most significant effect of surface texture. In the case of silicon carbide sliding against identical material in water, the experimental results indicate that surface texture is also helpful to improve the running-in progress to smooth the contact surfaces, showing another reason to result in low friction. Based on the consideration of enhancing the generation of hydrodynamic pressure and improving running-in progress, a surface texture pattern, which was combined with large (circle, 350 μm in diameter) and small (rectangular, 40 μm in length) dimples, was designed to maximize the texture effect on the load carrying capacity of SiC surfaces sliding in water. The friction coefficient of such textured surface was evaluated and compared with that of untextured and those only with large or small dimples only. The friction reduction mechanisms of the patterns with different dimples in size are discussed.     

Solid-state wetting on nanopatterned substrates

We review some recent results on the morphology of heteroepitaxial overlayers deposited on nanopatterned substrate surfaces. We mainly focus on modeling based on kinetic Monte Carlo (KMC) simulations. On arrays of parallel grooves or arrays of pillars, we find three main classes of states similar to those known for liquids: (i) Cassie–Baxter states, where solid islands sit on top of the substrate structure; (ii) Wenzel states, where solid islands are in contact with the bottom of the substrate; and (iii) solid imbibition (also denoted as capillary filling for parallel grooves), where the solid forms a film in the substrate surface structure. This multi-stability is controlled by the wettability parameter χ, and shape transitions exhibit hysteresis. We discuss the dynamics of the collapse of a Cassie–Baxter to Wenzel state, and the collapse of the Wenzel state to an imbibition film. We also discuss the possibility to grow crystals in the CB state on nanopatterned substrates. During growth, the crystals formed in CB state merge, leading to a continuous polycrystalline overlayer where the size of the grains is controlled by the distance between pillars.     

Variable focal lens controlled by an external voltage: An application of electrowetting

We use electrocapillarity in order to change the contact angle of a transparent drop, thus realizing a lens of variable focal length (B. Berge, J. Peseux, Patent deposited in Grenoble France, October 8th 1997, numéro d'enregistrement national 97 12781). The key point is the application of gradients of wettability, which control the shape of the drop edge, in our case a centered circle of variable radius. The quality and reversibility of the lens are surprisingly good. The optical power variation can be 5 to 10 times the one of the human eye, for a comparable diameter, with a typical response time of 0.03 s and a dissipated power of a few mW. Received 1 December 1999     

A Model for the Contact Angle of Liquid Droplets on Rough Surfaces

Up to now, measured results of the contact angle on rough surfaces have been explained usually based on the Wenzel equation （1936） and the Cassie-Baxter equation （1944）. However, these equations do not take into account considerations of liquid wetting behaviors on rough surfaces, and this leads to poor understanding of the mechanisms of contact between liquid droplets and rough surfaces （e.g. contact angle hysteresis）. We propose a new model for the contact angle of liquid droplets. By means of the present model, we can well understand the evperimental data which could not be well explained by the Wenzel equation and the Cassie-Baxter equation.     

Surface tension effects in the zero gravity inflow of a drop into a fluid

As a drop of fluid is deposited on the surface of a miscible fluid (that we call the solvent), it undergoes a strong pulling due to its surface rupture and it acquires a kinetic energy independently of gravity. For the drop and the solvent being of the same fluid we observe a drop injection at an initial velocity which scales as the square root of the surface tension of the drop against air. Once injected, the drop develops a transverse instability giving rise to an expanding ring. Viscosity terminates the process and stops the ring. We show that the final ring height follows a scaling law whereas two asymptotical scaling regimes can be identified for the ring radius. Received 31 August 1999     

纳米结构超疏水表面冷凝现象的三维格子玻尔兹曼方法模拟

采用三维多相流格子玻尔兹曼方法 (lattice Boltzmann method, LBM),对纳米结构超疏水表面液滴的冷凝行为进行模拟研究.通过Laplace定律和光滑表面的本征接触角理论对三维LBM模型进行定量验证.模拟分析了超疏水表面纳米阵列的几何尺寸和润湿性的局部不均匀性对冷凝液滴形核位置和最终润湿状态的影响规律.结果表明,较高的纳米阵列使液滴在纳米结构间隙的上部侧面和底部优先形核长大,通过采用上下不均匀的间隙可避免液滴在底部形核长大,而在上部侧面形核的冷凝液滴在生长过程中向上运动,其润湿状态由Wenzel态转变为Cassie态;较低的纳米阵列使液滴在纳米结构底部优先形核长大,液滴的最终润湿状态为Wenzel态;润湿性不均匀的纳米结构表面使液滴在阵列顶端亲水位置处优先形核长大,成为Cassie态.冷凝液滴在不同几何尺寸的纳米结构表面上的最终润湿状态的模拟结果与文献报道的实验结果符合良好.通过模拟还发现,冷凝液滴在生长过程中的运动行为与液滴统计平均作用力的变化有关.本文的LBM模拟再现了三维空间中液滴的形核、长大和润湿状态转变等物理现象.     

Suspended penetration wetting state of droplets on microstructured surfaces

When a water droplet on a micropillar-structured hydrophobic surface is submitted to gradually increased pressure, the CassieBaxter wetting state transforms into the Wenzel wetting state once the pressure exceeds a critical value. It has been assumed that the reverse transition(Wenzel-to-Cassie-Baxter wetting state) cannot happen spontaneously after the pressure has been removed.In this paper, we report a new wetting-state transition. When external pressure is exerted on a droplet in the Cassie-Baxter wetting state on textured surfaces with high micropillars to trigger the breakdown of this wetting state, the droplet penetrates the micropillars but does not touch the base of the surface to trigger the occurrence of the Wenzel wetting state. We have named this state the suspended penetration wetting state. Spontaneous recovery from the suspended penetration wetting state to the initial Cassie-Baxter wetting state is achieved when the pressure is removed. Based on the experimental results, we built models to establish the penetration depth that the suspended penetration wetting state could achieve and to understand the energy barrier that influences the equilibrium position of the liquid surface. These results deepen our understanding of wetting states on rough surfaces subjected to external disturbances and shed new light on the design of superhydrophobic materials with a robust wetting stability.     

A new model for thermodynamic analysis on wetting behavior of superhydrophobic surfaces

Superhydrophobic surfaces have shown inspiring applications in microfluidics, and self-cleaning coatings owing to water-repellent and low-friction properties. However, thermodynamic mechanism responsible for contact angle hysteresis (CAH) and free energy barrier (FEB) have not been understood completely yet. In this work, we propose an intuitional 3-dimension (3D) droplet model along with a reasonable thermodynamic approach to gain a thorough insight into the physical nature of CAH. Based on this model, the relationships between radius of three-phase contact line, change in surface free energy (CFE), average or local FEB and contact angle (CA) are established. Moreover, a thorough theoretical consideration is given to explain the experimental phenomena related to the superhydrophobic behavior. The present study can therefore provide some guidances for the practical fabrications of the superhydrophobic surfaces.     

Nanodroplets on rough hydrophilic and hydrophobic surfaces

We present results of Molecular Dynamics (MD) calculations on the behavior of liquid nanodroplets on rough hydrophobic and hydrophilic solid surfaces. On hydrophobic surfaces, the contact angle for nanodroplets depends strongly on the root-mean-square roughness amplitude, but it is nearly independent of the fractal dimension of the surface. Since increasing the fractal dimension increases the short-wavelength roughness, while the long-wavelength roughness is almost unchanged, we conclude that for hydrophobic interactions the short-wavelength (atomistic) roughness is not very important. We show that the nanodroplet is in a Cassie-like state. For rough hydrophobic surfaces, there is no contact angle hysteresis due to strong thermal fluctuations, which occur at the liquid-solid interface on the nanoscale. On hydrophilic surfaces, however, there is strong contact angle hysteresis due to higher energy barrier. These findings may be very important for the development of artificially biomimetic superhydrophobic surfaces.     

纳米结构表面上部分润湿液滴合并诱导弹跳的理论研究

部分润湿液滴是适宜纳米结构表面上滴状冷凝传热的主要载体,研究纳米结构参数与部分润湿液滴合并弹跳之间的关系有重要意义,本文依据冷凝液滴生长过程中能量增加最小的原理来判断其是否为部分润湿状态,并根据液滴合并前后的体积和界面自由能守恒,确定了合并液滴的初始形状,进而对合并液滴变形过程的动力学方程进行了求解,结果表明:部分润湿冷凝液滴仅在纳米柱具有一定高度、直径间距比较大的表面上形成,而当纳米柱高度过低、直径间距比小于0.1时则形成完全润湿的冷凝液滴;液滴合并后能否弹跳与纳米结构参数紧密相关,仅在纳米柱较高、直径间距比适宜的表面上,部分润湿液滴合并后才能诱发弹跳;液滴尺度及待合并液滴间的尺度比对合并弹跳也有重要影响;多个部分润湿液滴合并后由于具有更多的过剩界面自由能而比两个液滴合并更容易诱发弹跳,本模型对纳米结构表面上冷凝液滴是否合并诱发弹跳的计算结果与绝大部分实测结果相一致,准确率达到95%。     

Dewetting on porous media with aspiration

We consider a porous solid covered with a water film (or with a drop) in situations where the liquid is pumped in, either spontaneously (if the porous medium is hydrophilic) or mechanically (by an external pump). The dynamics of dewetting is then strongly modified. We analyse a few major examples, a) horizontal films, which break at a certain critical thickness, b) the “modified Landau-Levich problem” where a porous plate moves up from a bath and carries a film: aspiration towards the plate limits the height H reached by the film, c) certain situation where the hysteresis of contact angles is important. Received 5 October 1999 and Received in final form 7 February 2000     

A new model for the formation of contact angle and contact angle hysteresis

The formation mechanism of the contact angle and the sliding angle for a liquid drop on a solid surface plays an important role in producing hydrophobic surfaces. A new half soakage model is established in this paper as a substitute for Wenzel (complete soakage) and Cassie (no soakage) models. The model is suited to many solid surfaces, whether they are hydrophilic or hydrophobic, or even superhydrophobic. Based on the half soakage model, we analyse two surfaces resembling lotus, i.e. taper-like surface and corona-like surface. Furthermore, this new model is used to establish a quantitative relationship between the sliding angle and the parameters of surface morphology.     

Size and stability of liposomes: A possible role of hydration and osmotic forces

Dynamic light scattering and electrophoretic mobility measurements have been used to characterize the size, size distribution and zeta potentials (ζ-potentials) of egg yolk phosphatidylcholine (EYPC) liposomes in the presence of monovalent ions ( Na⁺ and K⁺). To study the stability of liposomes the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory has been extended by introducing the hydrated radius of the adsorbed ions onto the liposome surfaces. The decrease of liposome size is explained on the basis of the membrane impermeability to some ions which generate osmotic forces, which leads to evacuate water from liposome inside.     

The debate on the dependence of apparent contact angles on drop contact area or three-phase contact line: A review

A sessile drop is an isolated drop which has been deposited on a solid substrate where the wetted area is limited by the three-phase contact line and characterized by contact angle, contact radius and drop height. Although, wetting has been studied using contact angles of drops on solids for more than 200 years, the question remains unanswered: Is wetting of a rough and chemically heterogeneous surface controlled by the interactions within the solid/liquid contact area beneath the droplet or only at the three-phase contact line? After the publications of Pease in 1945, Extrand in 1997, 2003 and Gao and McCarthy in 2007 and 2009, it was proposed that advancing, receding contact angles, and contact angle hysteresis of rough and chemically heterogeneous surfaces are determined by interactions of the liquid and the solid at the three-phase contact line alone and the interfacial area within the contact perimeter is irrelevant. As a consequence of this statement, the well-known Wenzel (1934) and Cassie (1945) equations which were derived using the contact area approach are proposed to be invalid and should be abandoned. A hot debate started in the field of surface science after 2007, between the three-phase contact line and interfacial contact area approach defenders. This paper presents a review of the published articles on contact angles and summarizes the views of the both sides. After presenting a brief history of the contact angles and their measurement methods, we discussed the basic contact angle theory and applications of contact angles on the characterization of flat, rough and micropatterned superhydrophobic surfaces. The weak and strong sides of both three-phase contact line and contact area approaches were discussed in detail and some practical conclusions were drawn.     

Light trapping for a‐Si:H/µc‐Si:H tandem solar cells using direct pulsed laser interference texturing

We present a‐Si:H/µc‐Si:H tandem solar cells on laser textured ZnO:Al front contact layers. Direct pulsed laser interference patterning (DLIP) was used for writing arrays of one‐dimensional micro gratings of submicron period into ZnO:Al films. The laser texture provides good light trapping which is indicated by an increase in short‐circuit current density of 20% of the bottom cell limited device compared to cells on planar ZnO:Al. The open‐circuit voltage of the cells on laser textured ZnO:Al is almost the same as for cells on planar substrates, indicating excellent growth conditions for amorphous and microcrystalline silicon on the U‐shaped grating grooves. DLIP is a simple, single step and industrially applicable method for large area periodic texturing of ZnO:Al thin films. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)