Phase field modeling of hysteresis in sessile drops

We propose a novel approach to describe wetting of plane solid surfaces by liquid drops. A two-dimensional nonconserved phase field variable is employed to distinguish between wetted and nonwetted regions on the surface. The imbalance in the Young's force provides for the exchange of relative stability of the two phases. The three-phase contact line tension arises from the gradient energy and contact angle hysteresis from the kinetic coefficient. Using this theory, we discuss contact angle hysteresis on chemically heterogeneous surfaces. We show significant departure from the classical Cassie theory, which is attributed to defect pinning of the continuous triple line.     

Droplets on inclined rough surfaces

The behaviour of liquid droplets on inclined heterogeneous surfaces was simulated by the lattice-Boltzmann method using the Shan-Chen multiphase model. The effect of topography of the surface on the contact angle hysteresis was investigated. It is shown in particular, by using anisotropic rough surfaces, how surface topography and thereby the continuity of the three-phase contact line, affect this hysteresis. Our results clearly indicate that the superhydrophobicity of a surface cannot be judged by the contact angle alone.     

Lattice Boltzmann simulations of micron-scale drop impact on dry surfaces

A lattice Boltzmann equation (LBE) method for incompressible binary fluids is proposed to model the contact line dynamics on partially wetting surfaces. Intermolecular interactions between a wall and fluids are represented by the inclusion of the cubic wall energy in the expression of the total free energy. The proposed boundary conditions eliminate the parasitic currents in the vicinity of the contact line. The LBE method is applied to micron-scale drop impact on dry surfaces, which is commonly encountered in drop-on-demand inkjet applications. For comparison with the existing experimental results [H. Dong, W.W. Carr, D.G. Bucknall, J.F. Morris, Temporally-resolved inkjet drop impaction on surfaces, AIChE J. 53 (2007) 2606–2617], computations are performed in the range of equilibrium contact angles from 31° to 107° for a fixed density ratio of 842, viscosity ratio of 51, Ohnesorge number (Oh) of 0.015, and two Weber numbers (We) of 13 and 103.     

正癸烷纳米液滴润湿特性的分子动力学研究

流体液滴在固体表面的浸润性对其润滑性能至关重要.本文利用分子动力学方法研究了正癸烷纳米液滴在铜表面上的润湿特性.结果表明：在平坦光滑表面上,壁面的厚度和分子数目对润湿效果影响不大.随着壁面能量势阱参数εs 增大,接触角线性减小.随着温度升高,液滴的接触角减小.在沟槽粗糙表面上,随着粗糙度因子增大,对于疏液表面,接触角增大到一定值后基本保持不变,符合Cassie理论;中性和亲液表面接触角则会减小,为Wenzel润湿模式.当表面分数增大时,疏液与亲液表面接触角整体呈减小的趋势,对中性表面影响不大.当温度升高时,粗糙疏液表面接触角会增大,润湿效果更差,而粗糙中性和亲液表面液滴润湿性会更好.     

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     

Thoughts on some outstanding issues in the physics of equilibrium wetting and conceptual understanding of contact lines

Equilibrium wetting is a fundamental phenomenon, relevant to many scientific areas. Since the pioneering work on equilibrium wetting of Thomas Young (1805) [1], researchers strived to advance our understanding of this fundamental problem. Despite its apparent simplicity, equilibrium wetting phenomenon still holds many unanswered questions and represents a challenge to modern physicists and engineers. The relationship between quantities amenable to measurements, like macroscopic wetting contact angle, and other surface ener- gies and physical properties remains to be fully elucidated. Wetting is a physical problem which spans over two length scales, inner region (“microscopic”) length scale and outer region (“macroscopic”). The three-phase contact line, where the macroscopic region meets the micro- scopic one, and underlying surface forces, represents a challenge to fully understand and model. In this paper, a brief review of the basics of wetting and existing concepts is first presented. Then two important questions are discussed in the light of the latest experimental findings: first the relevance of the continuum concept when describing interfaces near the three-phase contact line, and second the effect of adsorption on interfacial energies and its use to explain some interesting observations like the dependence of equilibrium contact angle on pressure and size of droplets. These recent observations raise some fundamental questions about how the three-phase contact line is conceptualised.     

微矩形凹槽表面液滴各向异性浸润行为的研究

受自然界启发,仿生微结构被广泛用于调控固-液界面的性质.研究显示,液滴在微结构表面的各向异性浸润行为可用于实现微流动方向和速度的控制,且其各向异性浸润与微结构的尺寸和分布等密切相关.本文研究了微矩形凹槽尺寸对液滴各向异性浸润行为的影响规律.结果显示,液滴沿平行沟槽的方向具有较小的运动阻力、易铺展,因此具有较小接触角;而垂直于沟槽方向,由于沟槽的阻隔作用具有较大运动阻力,因而具有较大接触角,并且在垂直方向液滴的浸润过程是三相线一系列钉扎和跳跃行为.在微矩形凹槽表面,液滴沿平行方向接触角θ//与肋板宽度R和凹槽宽度G密切相关,其值与表面固体面积比成反比;而垂直于沟槽方向的接触角θ⊥随肋板宽度R和凹槽宽度G变化基本保持不变.同时各向异性液滴的变形比L/W、特征方向接触角比值θ⊥/θ//与表面固体面积比成正比.研究结果有助于加深理解微结构表面浸润行为的机制,并为微矩形凹槽在微流动控制方向的应用提供技术支持.     

Geometry-dependent electrostatics near contact lines

Long-ranged electrostatic interactions in electrolytes modify contact angles on charged substrates in a scale and geometry-dependent manner. For angles measured at scales smaller than the typical Debye screening length, the wetting geometry near the contact line must be explicitly considered. Using variational and asymptotic methods, we derive new transcendental equations for the contact angle as functions of the electrostatic potential only at the three phase contact line. Analytic expressions are found in certain limits and compared with predictions for contact angles measured with lower resolution. An estimate for electrostatic contributions to line tension is also given.     

The Surface Wettability and Adhesion of Poly(Ester Urethane)s and Poly(Ether Urethane)s

In this study the wetting characteristics of untreated and plasma-treated polyurethane thin films were investigated. The degree of wettability was investigated by measuring the contact angle formed between a liquid drop and the solid surface. The work of adhesion, interfacial free energy, spreading coefficient, and Girifalco–Good's interaction parameter changed significantly for plasma-treated polyurethane films. Both complete and partial wetting were analyzed from the spreading coefficient of liquid drops on the solid substrate.     

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.     

Molecular dynamics study of contact mechanics: contact area and interfacial separation from small to full contact

We report a molecular dynamics study of the contact between a rigid solid with a randomly rough surface and an elastic block with a flat surface. We study the contact area and the interfacial separation from small contact (low load) to full contact (high load). For small load the contact area varies linearly with the load and the interfacial separation depends logarithmically on the load. For high load the contact area approaches the nominal contact area (i.e., complete contact), and the interfacial separation approaches zero. The present results may be very important for soft solids, e.g., rubber, or for very smooth surfaces, where complete contact can be reached at moderate high loads without plastic deformation of the solids.     

基于Wenzel模型的粗糙界面异质形核分析

异质形核是形核发生的主要形式. 经典形核理论对基底界面作了理想化平面假设,然而实际异质形核体系中理想平直的固体界面是不存在的,这导致了异质形核描述与实际情况的偏差. 考察了固相晶胚在非平整界面上的异质形核过程,基于Wenzel润湿模型,分析了非理想界面的粗糙度因子对固相晶胚形核功的影响规律. 结果表明:当基底与晶核之间的本征润湿角小于90°时,基底界面越粗糙越有利于形核;本征润湿角大于90°时,基底界面越粗糙越不利于形核. 同时,游离晶胚在基底上润湿是球冠晶胚形成的重要途径,粗糙界面润湿过程中界面自由能的 关键词： 异质形核 粗糙界面 Wenzel模型 润湿过程     

接触角与液固界面热阻关系的分子动力学模拟

本文利用分子动力学方法模拟了液体在固体表面的 接触角及液固界面热阻, 并探讨了二者之间的关系. 通过分别改变液固结合强度和固体的原子性质来分析接触角和界面热阻的关系及变化趋势. 模拟结果显示增强液固间相互作用时, 接触角减小的同时界面热阻也随之单调减小; 而改变固体原子间结合强度和原子质量时, 接触角几乎保持不变, 但界面热阻显著改变. 固体原子间结合强度和原子质量影响界面热阻的原因是其改变了固体的振动频率分布, 导致液固原子间的振动耦合程度发生变化. 本文的结果表明界面热阻不仅与由接触角所表征的液固结合强度有关, 还与液固原子间的振动耦合程度有关. 接触角与界面热阻间不存在单值的对应关系, 不能单一地将接触角作为液固界面热阻的评价标准. 关键词： 液固界面 接触角 界面热阻 分子动力学模拟     

The apparent state of droplets on a rough surface

The factors influencing the state and wetting transition of droplets on a rough surface are both complex and obscure. The change in wetting is directly reflected by changes under the contact condition of the droplets with the surface. The recent study about the wettability of the superhydrophobic surface under the condensing condition arouses the new understanding about the apparent state of droplets on a rough surface. In this work, to validate the existence of droplets in an intermediate state, a microscale pillar topological polydimethylsiloxane (PDMS) surface was manufactured and its wettability under various conditions was studied. According to the experimental data, it is proposed that the wetting state of a rough surface may be embodied using the contact area ratio of a solid/liquid/gas droplet with the projective plane. A general calculation model for the apparent contact angle of droplets is given and expressed diagrammatically. It is found that the measured apparent contact angles of droplets at different states on the surface falls within the range predicted by our proposed equation. Supported by the National Natural Science Foundation of China (Grant No. 50606025)     

微液滴在不同能量表面上润湿状态的分子动力学模拟

微小液滴在不同能量表面上的润湿状态对于准确预测非均相核化速率和揭示界面效应影响液滴增长微观机理具有重要意义. 通过分子动力学模拟, 研究了纳米级液滴在不同能量表面上的铺展过程和润湿形态. 结果表明, 固液界面自由能随固液作用强度增加而增加, 并呈现不同液滴铺展速率和润湿特性. 固液作用强度小于1.6的低能表面呈现疏水特征, 继续增强固液作用强度时表面变为亲水, 而固液作用强度大于3.5的高能表面上液体呈完全润湿特征. 受微尺度条件下非连续、非对称作用力影响, 微液滴气液界面存在明显波动, 呈现与宏观液滴不同的界面特征. 统计意义下, 微小液滴在不同能量表面上铺展后仍可以形成特定接触角, 该接触角随固液作用强度增加而线性减小, 模拟结果与经典润湿理论计算获得的结果呈现相似变化趋势. 模拟结果从分子尺度为核化理论中的毛细假设提供了理论支持, 揭示了液滴气液界面和接触角的波动现象, 为核化速率理论预测结果和实验测定结果之间的差异提供了定性解释.     

Relationship between sliding acceleration of water droplets and dynamic contact angles on hydrophobic surfaces

This study measured sliding acceleration of water droplets on hydrophobic solid surfaces and used expanding and contracting method to compare that value with dynamic contact angles. Sliding action of the droplet was classified into three motion categories: constant accelerated motion, constant velocity and stasis. Differences exist in the dependencies of contact radius and the injection-suction rate in dynamic contact angle hysteresis according to these categories. This method is an effective indicator of water droplets’ sliding acceleration.     

A new laser shadowgraphy method for measurements of dynamic contact angle and simultaneous flow visualization in a sessile drop

A new laser shadowgraphy method is presented to measure the dynamic contact angle of a sessile drop on a nontransparent metal substrate and simultaneously visualize flow motions inside the drop. A collimated laser beam is refracted into the drop, then reflected on the substrate surface and finally refracted out of the drop to form a shadowgraphic image on a screen. The instant diameters of the refracted-shadowgraphic image, cooperated with the corresponding instant contact-diameters of the drop measured from the magnified top view, are used to determine the instant contact angles of the sessile drop. At the same time, flow motions, if any, in the drop can be visualized from the refracted-shadowgraphic image. The new method is demonstrated to be a very simple, accurate, and unique optical technique for simultaneous measuring of the dynamic contact angle of a liquid drop spreading on a nontransparent metal substrate with flow visualization in the drop.     

Wetting behaviour of plasma sprayed oxide coatings

Wetting behaviour of several plasma sprayed oxide surfaces were characterised using contact angle measurements. Since surfaces contained pores and cracks, the evaluation of wetting angles led only to rough estimation of surface free energies. In order to find out the effect of atmospheric contamination the wetting behaviour of plasma-etched surfaces was followed as a function of time.It was found out that the sample preparation method had great influence on the contact angle of plasma sprayed oxide surfaces. The contact angle of plasma-etched surfaces increased when the surfaces were exposed to air. The probable reason for that was adsorption of low surface free energy contaminants to the sample surfaces.