液滴在梯度微结构表面上的铺展动力学分析

本文通过改变肋柱宽度和间距, 构造了二级和多级梯度微结构表面, 采用格子-Boltzmann方法对液滴在两种梯度表面上的铺展过程进行了研究, 探析液滴运动的机理和调控方法. 结果表明, 在改变肋柱间距的二级梯度表面上, 当液滴处于Cassie态时, 接触角滞后大小与粗糙度梯度成正比关系; 当液滴从Cassie态转换为Wenzel态或介于两者之间的不稳定态时, 这一正比关系不再遵循. 在改变肋柱宽度的二级梯度表面上, 接触角滞后大小与粗糙度梯度始终成正比关系. 在多级梯度表面上, 随液滴初始半径增大, 接触角滞后减小, 但液滴平衡位置相较于初始位置偏离增大. 对梯度微结构表面上液滴运动和接触角滞后的定量分析, 可为实现梯度微结构表面液滴运动调控提供理论依据.     

平衡接触角对受热液滴在水平壁面上铺展特性的影响

壁面温度是影响壁面润湿性的重要外部条件. 为解决液滴铺展中三相接触线处应力集中问题, 已有研究多采用预置液膜假设, 但无法探究壁面温度对润湿性的影响. 本文针对受热液滴在固体壁面上的铺展过程, 基于润滑理论建立了演化模型, 通过数值模拟, 从平衡接触角角度分析了温度影响壁面润湿性及铺展过程的内部机理. 研究表明: 随温度梯度增大, 液滴所受Marangoni效应增强, 致使液滴向低温区的铺展速率加快; 铺展过程中, 位于高温区的接触线与液滴主体部分间形成一层薄液膜, 重力与热毛细力先后主导该区域的铺展; 当液-固或气-液界面张力对温度的敏感度高于另两个界面时, 低温区方向的平衡接触角不断增大, 使壁面润湿性恶化, 导致液滴铺展减慢; 而当气-固界面张力对温度的敏感度高于其他两个界面时, 低温区方向上的平衡接触角将减小, 由此改善壁面润湿性, 加快液滴铺展; 在温度影响壁面润湿性和液滴铺展过程中, 平衡接触角起关键作用.     

接触角滞后现象的理论分析

在本文的研究中，考虑表面粗糙的影响，通过引入附加“磨擦力”的概念，分别用力学方法和热力学方法导出固体表面上液滴平衡时接触角应满足的条件；并得到了液滴系统自由能－固液接触面积曲线；分析了前进接触角和后退接触角的物理意义；由此给出了接触角滞后现象的一种合理解释．这对于进一步认识接触角的滞后现象，无疑是有积极意义的．     

溶液液滴蒸发变干的环状沉积

液体蒸发驱动的颗粒自组装现象在许多的工业技术中有重要应用. 本文利用显微镜观测含有颗粒物质的液滴变干后留在固体表面的颗粒形成的环状沉积图案. 采用微米粒径的SiO₂小球水溶液液滴蒸发变干模拟咖啡环的形成过程, 结果发现液滴蒸发过程中接触线的钉扎是环状沉积的必要条件. 在液滴蒸发过程中颗粒随着补偿流不断的向液滴边缘移动, 聚集在接触线处形成环. 液滴蒸发变干后残留在液滴内部的颗粒数随颗粒质量分数的增加而增加, 可以达到单层的颗粒排列. 而玻璃衬底上的颗粒环在颗粒质量分数很小时, 形成单层排列, 且一排一排地生长. 蒸发过程中颗粒环由于液滴边缘的尺寸限制向液滴中心缓慢移动. 这会导致液滴中不同大小颗粒的分离. 关键词： 液滴 接触线 蒸发 颗粒     

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.     

Simulation solution for micro droplet impingementon a flat dry surface

This paper presents a computational fluid dynamics approach for micro droplet impacting on a flat dry surface. A two-phase flow approach is employed using FLUENT VOF multiphase model to calculate the flow distributions upon impact. The contact line velocity is tracked to calculate the dynamic contact angle through user defined function program. The study showed that the treatment of contact line velocity is crucial for the accurate prediction of droplet impacting on poor wettability surfaces. On the other hand, it has much less influence on the simulation of droplet impacting on good wettability surfaces. Good fit between simulation results and experimental data is obtained using this model.     

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.     

微液滴在超疏水表面的受迫振动及其接触线的固着-移动转变

利用高速摄影技术对超疏水表面液滴振动的动态行为进行观测,研究液滴在不同频率下的振动特性. 实验发现,液滴的共振频率满足Rayleigh方程,微液滴在超疏水表面具有自由液滴的振动性质. 在80–200 Hz的驱动频率范围内,接触线出现了明显的固着-移动现象,液滴的振动频率是驱动频率的一半,液滴振动时的形变较大. 当驱动频率大于200 Hz时,接触线基本固着,液滴的振动频率近似等于驱动频率,液滴共振时的形态边缘始终有节点存在. 分析表明,液滴对外界驱动的不同响应与接触线的振荡行为和变形程度密切相关 关键词： 超疏水表面 受迫振动 共振 接触线     

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.     

Evaporation of liquid droplets from a surface of anodized aluminum

The results of study of evaporation of water droplets and NaCl salt solution from a solid substrate made of anodized aluminum are presented in this paper. The experiment provides the parameters describing the droplet profile: contact spot diameter, contact angle, and droplet height. The specific rate of evaporation was calculated from the experimental data. The water droplets or brine droplets with concentration up to 9.1 % demonstrate evaporation with the pinning mode for the contact line. When the salt concentration in the brine is taken up to 16.7 %, the droplet spreading mode was observed. Two stages of droplet evaporation are distinguished as a function of phase transition rate.     

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.     

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     

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.     

Lateral vibration of a water drop and its motion on a vibrating surface

The resonant modes of sessile water drops on a hydrophobic substrate subjected to a small-amplitude lateral vibration are investigated using computational fluid dynamic (CFD) modeling. As the substrate is vibrated laterally, its momentum diffuses within the Stokes layer of the drop. Above the Stokes layer, the competition between the inertial and Laplace forces causes the formation of capillary waves on the surface of the drop. In the first part of this paper, the resonant states of water drops are illustrated by investigating the velocity profile and the hydrostatic force using a 3d simulation of the Navier-Stokes equation. The simulation also allows an estimation of the contact angle variation on both sides of the drop. In the second part of the paper, we investigate the effect of vibration on a water drop in contact with a vertical plate. Here, as the plate vibrates parallel to gravity, the contact line oscillates. Each oscillation is, however, rectified by hysteresis, thus inducing a ratcheting motion to the water droplet vertically downward. Maximum rectification occurs at the resonant states of the drop. A comparison between the frequency-dependent motion of these drops and the variation of contact angles on their both sides is made. The paper ends with a discussion on the movements of the drops on a horizontal hydrophobic surface subjected to an asymmetric vibration.     

Vibrations of sessile drops

This study focuses on the effects of vertical vibrations on sessile drops deposited on hydrophobic substrates. At low amplitudes the contact line remains pinned because of contact angle hysteresis and only drop surface modes areobserved. Above a first threshold the contact line starts to move and exhibits a stick-slip behavior that presents some analogies with the solid friction on amechanical oscillator. At larger amplitudes, non-axisymmetric contour modes show up (modes m=2, 3...). They can be interpreted as a coupling between surface modes and contact line motion. These subharmonic modes are welldescribed within the framework of parametric oscillators. We also discuss here why vibrations can help to measure equilibrium contact angle.     

Nonlinear dependence of the contact angle of nanodroplets on contact line curvature

We have measured the contact angle of microsized and nanosized alkane droplets partially wetting a model substrate using true noncontact atomic force microscopy. The large range of droplet sizes accessible using this technique allowed us to determine the contact line curvature dependence of the contact angle with unprecedented accuracy. Whereas previous studies aimed at explaining such a dependence by a line tension effect, our results and calculations on a model system exclude such an effect and point to an extreme sensitivity to weak substrate heterogeneities confirmed by numerical simulations.     

Contact angle hysteresis on nano-structured surfaces

We present results from an experimental study on the phenomenon of contact angle hysteresis on solid surfaces decorated by a random array of nanometric hollows. For weak values of the areal density of defects φ_d, the hysteresis H increases linearly with φ_d. This evolution is described by a pinning–depinning process of the contact line by individual defects. At higher values of φ_d, a collective pinning effect appears and H decreases with increasing φ_d. In the linear regime, our experimental results are compared to theoretical predictions for contact angle hysteresis induced by a single isolated defect on the solid surface. We suggest that the crossover from the individual to the collective pinning effects could be interpreted in terms of an overlapping of wetting cross sections. Finally, we analyse the influence of both the size and the morphology (hollows/hillocks) of defects on the anchorage of the contact line.     

带凹槽的微通道中液滴运动数值模拟

运用改进的耗散粒子动力学方法模拟了液滴在由凹槽所构成的粗糙表面微通道内的运动行为.改进的耗散粒子动力学方法采用新近提出的一种短程排斥、长程吸引相互作用势能函数,从而可以模拟带有自由面的流体,如液滴等.模拟了新势能函数下液滴与固体壁面的静态接触角,并用2次多项式拟合了"接触角-a_wf/a_f"变化曲线.研究了液滴在带凹槽的微通道中运动时,微通道壁面浸润性、外场力、液滴温度对液滴流动特性的影响.研究表明壁面浸润性和外场力对液滴流动特性的影响较大,液滴温度对液滴流动特性的影响较小.研究结果对运用耗散粒子动力学方法模拟并分析微流体在复杂微通道的流动有一定的参考价值.     

Pinning-depinning of the contact line on nanorough surfaces

We study the pinning-depinning phenomenon of a contact line on a solid surface decorated by a random array of nanometric structures. For this purpose, we have investigated the contact angle hysteresis behaviour of six different wetting and non-wetting fluids with surface tensions varying from 25 to 72mN m^-1. For low values of the areal density of defects φ_d, the hysteresis H increases linearly with φ_d indicating that “individual” defects pin the contact line. Then, from a given value of φ_d, the hysteresis H becomes to decrease with increasing φ_d, indicating a new kind of collective depinning. These two regimes were observed for all fluids used. In both cases, our experimental results are compared with the theoretical predictions for contact angle hysteresis induced by single or multiple topographical defects. We ascribe the decrease of H to the formation of cavities along the wetting front.     

Estimating critical surface tension from droplet spreading area

Critical surface tension (CST) is a measure of solid surface tension and is mainly determined by measuring the contact angle of a droplet on a target solid surface. The concept of CST makes it possible to determine solid surface tension without any unprovable assumptions such as the Fowkes hypothesis. However, it requires somewhat special devices and skills for measuring the contact angle. In this work, we propose a simple method to determine the CST of a solid by measuring the droplet spreading area. This method is developed by combining the conventional CST with a simple analytical droplet model. The difference in estimated CSTs between our method and the conventional one is within 3.0%. Our method enables a quick and simple evaluation of the solid surface tension without special devices for measuring the contact angle.