We discuss the equilibrium condition for a liquid that partially wets a solid on the level of intermolecular forces. Using a mean field continuum description, we generalize the capillary pressure from variation of the free energy and show at what length scale the equilibrium contact angle is selected. After recovering Young's law for homogeneous substrates, it is shown how hysteresis of the contact angle can be incorporated in a self-consistent fashion. In all cases the liquid-vapor interface takes a nontrivial shape, which is compared to models using a disjoining pressure.
Following Gibb's interpretation of an interface as a dividing surface, we derive a model for the microscopic dynamic contact angle by writing a force balance for a control volume encompassing the interfaces and the contact line. In doing so we identify that, in addition to the surface tension of respective interfaces, the gradient of surface tension plays an important role in determining the dynamic contact angle. This is because not only does it contribute towards an additional force, but it also accounts for the deviation of local surface tension from its static equilibrium value. It is show…
The fluid-mechanics community is currently divided in assessing the boundaries of applicability of the macroscopic approach to fluid mechanical problems. Can the dynamics of nano-droplets be described by the same macroscopic equations as the ones used for macro-droplets? To the greatest degree, this question should be addressed to the moving contact-line problem. The problem is naturally multiscale, where even using a slip boundary condition results in spurious numerical solutions and transcendental stagnation regions in modelling in the vicinity of the contact line. In this publication, it ha…
It is common to relate the dynamic contact angle $θ_d$ to the relative speed between the substrate and the contact line; theory suggests $θ_d^3 \propto U$. In fact, available physical models show that the dynamic angle involves speed logarithmically and in a model dependent manner. Experimental data consistent with this interpretation is cited.
Applying contact angles based on a continuously moving contact line in 2D VOF simulations
University of Chinese Academy of Sciences（中国科学院大学）；Sorbonne Université（索邦大学）；Xi’an Jiaotong University（西安交通大学）；Institut Universitaire de France（法国高等学术研究院）
Equilibrium contact angle of liquid drops over horizontal surfaces has been modeled using Smoothed Particle Hydrodynamics (SPH). The model is capable of accurate implementation of contact angles to stationary and moving contact lines. In this scheme, the desired value for stationary or dynamic contact angle is used to correct the profile near the triple point. This is achieved by correcting the surface normals near the contact line and also interpolating the drop profile into the boundaries. Simulations show that a close match to the chosen contact angle values can be achieved for both station…
The contact angle between a gas-liquid interface and a solid surface is a function of the dynamic conditions of the contact line. Classic steady correlations link the contact angle to the contact line velocity. However, it is not clear whether they hold in presence of inertia and in the case of perfect wetting fluids. We analyze the shape of a liquid interface and the corresponding contact angle in accelerating conditions for two different fluids, i.e. HFE7200 (perfect wetting) and demineralized water. The set-up consists of a U-shaped quasi-capillary tube in which the liquid column oscillates…
A dynamic wetting problem is studied for a moving thin fiber inserted in fluid and with a chemically inhomogeneous surface. A reduced model is derived for contact angle hysteresis by using the Onsager principle as an approximation tool. The model is simple and captures the essential dynamics of the contact angle. From this model we derive an upper bound of the advancing contact angle and a lower bound of the receding angle, which are verified by numerical simulations. The results are consistent with the quasi-static results. The model can also be used to understand the asymmetric dependence of…
We consider a liquid drop placed on a smooth homogeneous solid substrate as it spreads from rest to its eventual equilibrium state. The problem is studied numerically in the framework of a model where the contact angle formed by the drop's free surface with the substrate is not prescribed as a function of the contact-line speed and has to be found as part of the solution. It is shown that in this spontaneous spreading, as the drop starts moving and the contact line accelerates, the dynamic contact angle decreases with the contact-line speed, which is in line with what experimental observations…
We investigate directly at the microscale the morphology of the electrowetting induced transition between the Cassie-Baxter and Wenzel states for a water droplet on a superhydrophobic surface. Our experiments demonstrate that the transition originates in a very narrow annular region near the macroscopic contact line, which is first invaded by water and causes a thin film of air to be entrapped below. At high applied voltages, a growing fraction of microscopic air-pockets collapse, resulting in a partialWenzel state. Modulations in the intensity of the light reflected from individual micro-meni…
We investigate the moving contact line problem for two-phase incompressible flows with a kinematic approach. The key idea is to derive an evolution equation for the contact angle in terms of the transporting velocity field. It turns out that the resulting equation has a simple structure and expresses the time derivative of the contact angle in terms of the velocity gradient at the solid wall. Together with the additionally imposed boundary conditions for the velocity, it yields a more specific form of the contact angle evolution. Thus, the kinematic evolution equation is a tool to analyze the …
In this paper, we applied the Shan-Chen multiphase Lattice Boltzmann method to simulate two different parameters, contact angle (a static parameter) and slip length (a dynamic parameter), and we proposed a relationship between them by fitting those numerical simulation results. By changing the values of the strength of interaction between fluid particles (SIF) and the strength of interaction between fluid and solid surface (SIFS), we simulated a series of contact angles and slip lengths. Our numerical simulation results show that both SIF and SIFS have little effects on the relationship betwee…
The moving contact-line problem is of both theoretical and practical interest. The dynamic contact angle changes with the capillary number defined by the contact-line speed, and the correlation also depends on the equilibrium contact angle measured at the static state. This correlation is usually required as an input to the traditional solvers based on the Navier-Stokes-like equations, but it is simulated as an output in the current study using the lattice Boltzmann method (LBM) in a displacement process of two-immiscible fluids. The macroscopic theory and the molecular dynamics (MD) simulatio…
Micropatterned surfaces composed of concentric circular defects having a smooth trench-like profile are formed using a photoresist (SU-8). When an evaporating droplet encounters the micropatterned surface an evaporation phase is observed consisting of distinct discontinuities and steps in the droplet wetting contact angle and base radius respectively. The addition of gaps into the circular defects enables tuning of the contact angle hysteresis; the receding contact angle of fluorocarbon coated SU-8 can be tuned between 34.6° and 89.1° and that of SU-8 surfaces from 5.6° to 43.3° depending on t…
Using as a starting point conservation of momentum, a multiphase mechanical energy balance equation is derived that accounts for multiple material phases and interfaces present within a moving control volume. This balance is applied to a control volume that is anchored to a three phase contact line as it advances over the surface of a rough and chemically homogeneous solid. Using semi-quantitative models for the material behaviour occurring within the control volume, an order-of-magnitude analysis is performed to find what terms within the balance are significant, producing an equation that ca…
The surface of a liquid near a moving contact line is highly curved owing to diverging viscous forces. Thus, microscopic physics must be invoked at the contact line and matched to the hydrodynamic solution farther away. This matching has already been done for a variety of models, but always assuming the limit of vanishing speed. This excludes phenomena of the greatest current interest, in particular the stability of contact lines. Here we extend perturbation theory to arbitrary order and compute finite speed corrections to existing results. We also investigate the impact of the microscopic phy…
The spreading of an incompressible viscous liquid over an isotropic homogeneous unsaturated porous substrate is considered. It is shown that, unlike the dynamic wetting of an impermeable solid substrate, where the dynamic contact angle has to be specified as a boundary condition in terms of the wetting velocity and other flow characteristics, the `effective' dynamic contact angle on an unsaturated porous substrate is completely determined by the requirement of existence of a solution, i.e. the absence of a nonintegrable singularity in the spreading fluid's pressure at the `effective' contact l…
The contact angle that a liquid drop makes on a soft substrate does not obey the classical Young's relation, since the solid is deformed elastically by the action of the capillary forces. The finite elasticity of the solid also renders the contact angles different from that predicted by Neumann's law, which applies when the drop is floating on another liquid. Here we derive an elasto-capillary model for contact angles on a soft solid, by coupling a mean-field model for the molecular interactions to elasticity. We demonstrate that the limit of vanishing elastic modulus yields Neumann's law or a…
The molecular structure of moving contact lines (MCLs) and the emergence of a corresponding macroscopic dissipation have made the MCL a paradigm of fluid dynamics. Through novel averaging techniques that remove capillary waves smearing we achieve an unprecedented resolution in molecular dynamics (MD) simulations and find that they match with the continuum description obtained by finite element method (FEM) down to molecular scales. This allows us to distinguish dissipation at the liquid-solid interface (Navier-slip) and at the contact line, the latter being negligible for the rather smooth sub…
Static contact angle hysteresis (CAH) is widely attributed to surface roughness and chemical contamination. In the latter case, chemical defects create free-energy barriers that prevent the contact line motion. Electrowetting studies have demonstrated the similar ability of electric fields to alter the surface free-energy landscape. Yet, the increase of apparent static CAH by electric fields remains unseen. Here, we report the observation and theoretical analysis of electrowetting hysteresis. This phenomenon enables the continuous and dynamic control of CAH, not only for fundamental studies bu…
Oscillation of sessile drops is important to many applications. In the present study, the natural oscillation of a sessile drop on flat surfaces with free contact lines (FCL) is investigated through numerical and theoretical analysis. The FCL condition represents a limit of contact line mobility, i.e. the contact angle remains constant when the contact line moves. In the numerical simulation, the interfaces are captured by the volume-of-fluid method and the contact angle at the boundary is specified using the height-function method. The oscillation frequencies for sessile drops with FCL are ma…
The present work investigates the role of contact angle hysteresis at the liquid-liquid-solid interface (LLS) on the rod climbing effect of two immiscible Newtonian liquids using experimental and numerical approaches. Experiments revealed that the final steady state contact angle, $θ_{w}$ at the LLS interface varies with the rod rotation speed, $ω$. For the present system, $θ_{w}$ changes from $\sim$69$^{\circ}$ to $\sim$83$^{\circ}$ when the state of the rod is changed from static condition to rotating at 3.3 Hz. With further increase in $ω$, the $θ_{w}$ exceeds 90$^{\circ}$ which cannot be o…
The evaporation of sessile drops in quiescent air is usually governed by vapour diffusion. For contact angles below $90^\circ$, the evaporative flux from the droplet tends to diverge in the vicinity of the contact line. Therefore, the description of the flow inside an evaporating drop has remained a challenge. Here, we focus on the asymptotic behaviour near the pinned contact line, by analytically solving the Stokes equations in a wedge geometry of arbitrary contact angle. The flow field is described by similarity solutions, with exponents that match the singular boundary condition due to evap…
Microfluidics technology offers high efficiency of heat and mass transfer and low safety hazards compared to conventional multiphase processes. The multiphase flow in the microchannels is usually characterized as Taylor flow that includes elongated microbubbles , separated by liquid slugs. In the current study, we employ OpenFOAM CFD package to investigate the effect of the surface tension and the contact angle on the interfacial surface area and transport yield in microscale systems. The results show that contact angle can significantly affect the surface area and the bubble size while the su…
An arbitrary Lagrangian--Eulerian (ALE) finite element scheme for computations of soluble surfactant droplet impingement on a horizontal surface is presented. The numerical scheme solves the time-dependent Navier--Stokes equations for the fluid flow, scalar convection-diffusion equation for the surfactant transport in the bulk phase, and simultaneously, surface evolution equations for the surfactants on the free surface and on the liquid-solid interface. The effects of surfactants on the flow dynamics are included into the model through the surfactant-dependent surface tension and dynamic cont…
Evaporation of water droplets on a superhydrophobic substrate, on which the contact line is pinned, is investigated. While previous studies mainly focused on droplets with contact angles smaller than 90^\circ, here we analyze almost the full range of possible contact angles (10^\circ -150^\circ). The greater contact angles and pinned contact lines can be achieved by the use of superhydrophobic Carbon Nanofiber substrates. The time-evolutions of the contact angle and the droplet mass are examined. The experimental data is in good quantitative agreement with the model presented by Popov (Physica…
We study the contact angle hysteresis and morphology changes of a liquid drop sitting on a solid substrate inclined with respect to the horizontal at an angle $α$. This one is always smaller than the critical one, $α_{crit}$, above which the drop would start to slide down. The hysteresis cycle is performed for positive and negative $α$'s ($|α|<α_{crit}$), and a complete study of the changes in contact angles, free surface and footprint shape is carried out. The drop shape is analyzed in terms of a solution of the equilibrium pressure equation within and out of the long--wave model (lubrication…
Given the importance of dynamic contact angle, its numerous applications and the complexity and difficulty of use of available approaches, here we present a new simple semi-empirical models for estimation of dynamic contact angle's dependence on the wetting line velocity. These models should be applicable to any geometry, a very large range of capillary numbers and static contact angles and all solid-liquid-gas systems without requiring further experiments. Two simple equations are intuitively derived from the most promising theoretical dynamic contact angle models, the hydrodynamic and the mo…
Surface tension and contact angle measurements are fundamental characterization techniques relevant to thermal and fluidic applications. Drop shape analysis techniques for the measurement of interfacial tension are powerful, versatile and flexible. Here we develop a Spline-based Interface Modeling and Optimization (SIMO) tool for estimating the surface tension and the contact angle from the profiles of sessile and pendant drops of various sizes. The employed strategy models the profile using a vector parametrized cubic spline which is then evolved to the eventual equilibrium shape using a nove…
In this paper, we present a computationally efficient method for including fluid-solid interactions into direct numerical simulations of the Navier-Stokes equations. This method is found to be as powerful as our earlier formulation [J. Comp. Phys., vol. 249: 243 (2015)], while outperforming the earlier method in terms of computational efficiency. The performance and efficacy of the presented method are demonstrated by computing contact angles of droplets at equilibrium. Furthermore, we study the instability of films due to destabilizing fluid-solid interactions, and discuss the influence of co…
In this work, the motion of a 2-D drop on a surface with given wettability gradient is studied numerically by a hybrid lattice-Boltzmann finite-difference method using the multiple-relaxation-time collision model. We incorporate the geometric wetting boundary condition that allows accurate implementation of a contact angle hysteresis model. The method is first validated through three benchmark tests, including the layered Poiseuille flow with a viscosity contrast, the motion of a liquid column in a channel with specified wettability gradient and the force balance for a static drop attached to …
We construct a novel model for the steady-state contact angles of liquid droplets at the wetted substrate. The non-removable, thin liquid film covering the substrate is governed by the intermolecular forces between molecules of liquid and solid, which we describe using the standard disjoining pressure approximation. Balancing the disjoining pressure against the surface tension we find the smooth shape of the surface of the liquid. We show that we can extract an effective contact angle from the region where the film and the droplet meet. Crucially, we find that for large droplets the contact an…
The profiles of a spreading wetting film are computed taking into account intermolecular forces and introducing a kinetic slip condition at a molecular cut-off distance. This eliminates the stress singularity, so that both "true" and "visible" contact angles are defined unequivocally. The "true" contact angle at the cut-off distance depends on the slip length as well as on the edge propagation speed, but not on gravity or asymptotic inclination angle. These macroscopic factors influence, however, the "visible" contact angle observed in the interval where the actual film profile departs from th…
Displacement of floating polymer (polyolefin) rafts by steady magnetic field is reported. The effect is due to the interplay of gravity deforming the water/vapor interface, contact angle hysteresis and diamagnetic properties of the liquid support. Magnetic field (ca. 0.06 T) deformed the water/vapor interface and impacted the interfacial apparent contact angle. This deformation gave rise to the propulsion force, displacing the polymer raft. The velocity of displacement of the center of mass of rafts was registered. The effect is related to the contact angle hysteresis affected by the magnetic …
Contact angle is an important parameter in characterizing the wetting properties of fluids. The most common methods for measuring the contact angle is to measure it directly from the profile curve of a sessile drop, a method with certain inherent drawbacks. Here we describe an alternative method that uses the height and volume of a sessile drop as constraints to construct its profile by numerical integration of its two governing differential equations. The integration yields, self consistently, the average value of the contact angle along the entire contact line as well as the footprint radius…
We theoretically investigate the apparent contact angle of droplets on liquid infused surfaces as a function of the relative size of the wetting ridge and the deposited droplet. We provide an intuitive geometrical interpretation whereby the variation in the apparent contact angle is due to the rotation of the Neumann triangle. We also derive linear and quadratic corrections to the apparent contact angle as power series expansion in terms of pressure differences between the lubricant, droplet and gas phases. These expressions are much simpler and more compact compared to those previously derive…
Passive droplet transport mechanisms, in which continuous external energy input is not required for motion, have received significant attention in recent years. Experimental studies of such mechanisms often ignore, or use careful treatments to minimize, contact angle hysteresis, which can impede droplet motion, or even arrest it completely. Here, we consider the effect of contact angle hysteresis on bendotaxis, a mechanism in which droplets spontaneously deform an elastic channel via capillary pressure and thereby move. Here, we seek to understand when contact angle hysteresis prevents bendota…
Contact angle is an essential physical quantity that characterizes the wettability of a substrate. Although it is widely used in the studies of surface wetting, capillary phenomena and moving contact lines, measuring contact angles in experiments and simulations is still complicated and time-consuming. In this paper, we present an efficient scheme for the real-time and on-the-spot measurement of contact angles on curved wetting surfaces in lattice Boltzmann simulations. The measuring results are in excellent agreement with the theoretical predictions by the spherical cap method without conside…
New exact solutions for the evaporation flux density of a small droplet on a flat horizontal substrate with a contact angle in the range of 135-180 degrees
The pinning of the contact line adversely influences the electrowetting performance of sessile liquid droplets. In this paper, we report the electrowetting hysteresis characteristics of 100 mM aq. KCl sessile liquid droplet placed on a hydrophobic PDMS surface. The effect of nanoparticles on the contact angle hysteresis under the imposed electric potential is further investigated. This study reveals that the contact angle hysteresis decreases beyond a certain threshold value of nanoparticles concentration. Therefore, nanoparticle suspension in the liquid droplet can be used to enhance or suppr…
The prevailing models for advancing dynamic contact angle are under intensive debates, and the fitting performances are far from satisfying in practice. The present study proposes a model based on the recent understanding of the multi-scale structure and the local friction at the contact line. The model has unprecedented fitting performance for dynamic contact angle over wide spreading speed regime across more than five orders of magnitude. The model also well applies for non-monotonous angle variations which have long been considered as abnormal. The model has three fitting parameters, and tw…
We study the nanoscale behaviour of the density of a simple fluid in the vicinity of an equilibrium contact line for a wide range of Young contact angles between 40 and 135 degrees. Cuts of the density profile at various positions along the contact line are presented, unravelling the apparent step-wise increase of the film height profile observed in contour plots of the density. The density profile is employed to compute the normal pressure acting on the substrate along the contact line. We observe that for the full range of contact angles, the maximal normal pressure cannot solely be predicte…
Electrowetting of nanodrops is studied for aqueous electrolyte mixtures. We report a new method for controlling the degree of deformation and minimum attainable contact angle by varying the difference of solvation strengths between the two solvents, which determines the ratio of ion concentrations. This implies that the commonly observed saturation of the contact angle with the applied electric field can be suppressed by increasing the solvation energy difference, a finding of practical significance for micro and nanofluidics. Saturation is traced to be caused by the transfer of ions from the …
We account for the presence of surface charges towards describing variations in the dynamic contact angle of an advancing liquid-gas meniscus. Starting from the thin-film based formalism, we present closed-form analytical expressions relating the dynamic contact-angle with the capillary number (essentially normalized contact-line speed) and other interfacial parameters. Specifically, our analysis presents, within the realm of hydrodynamic paradigm, a connection between the micro- and macro-scale physics at the vicinity of the contact-line region, taking the combined confluence of viscous and c…
Recent experiments (Guan et al. 2016a,b) showed many interesting phenomena on dynamic contact angle hysteresis while there is still a lack of complete theoretical interpretation. In this work, we study the time averaging of the apparent advancing and receding contact angles on surfaces with periodic chemical patterns. We first derive a Cox-type boundary condition for the apparent dynamic contact angle on homogeneous surfaces using Onsager variational principle. Based on this condition, we propose a reduced model for some typical moving contact line problems on chemically inhomogeneous surfaces…
In this paper, we aim to investigate the implementation of contact angles in the pseudopotential lattice Boltzmann modeling of wetting at a large density ratio. The pseudopotential lattice Boltzmann model [X. Shan and H. Chen, Phys. Rev. E 49, 2941 (1994)] is a popular mesoscopic model for simulating multiphase flows and interfacial dynamics. In this model, the contact angle is usually realized by a fluid-solid interaction. Two widely used fluid-solid interactions: the density-based interaction and the pseudopotential-based interaction, as well as a modified pseudopotential-based interaction f…
In this paper, we propose an alternative approach to implement the contact angle boundary condition on immersed surfaces for phase-field simulations of two-phase flows using the Cahn-Hilliard equation on a Cartesian mesh. This simple and effective method was inspired by previous works on the geometric formulation of the wetting boundary condition. In two dimensions, by making full use of the hyperbolic tangent profile of the order parameter, we were able to obtain its unknown value at a ghost point from the information at only one point in the fluid. This is in contrast with previous approache…
Wetting phenomena play a key role in flows through porous media. Relative permeability and capillary pressure-saturation functions show a high sensitivity to wettability, which has different definitions at the continuum- and pore-scale. At the continuum-scale, the state of wetting is defined as Amott-Harvey or USBM (United States Bureau of Mines) by capillary pressure drainage and imbibition cycles. At the pore-scale, the concept of contact angle is used, which until recently was not experimentally possible to determine within an opaque porous medium. Recent progress on measurements of pore-sc…
We predict the volume of liquid recovered from different-shaped prismatic channels following gas displacement. This recovery factor depends strongly on the contact angle at which the gas-liquid interfaces meet the walls of the channel. We show that scaling the contact angle by a critical value, dependent on the channel shape, leads to a master curve for the recovery factor.} Our numerical simulations with the Surface Evolver are supported by theoretical calculations for the capillary entry pressure in a channel with a triangular or rectangular cross-section and for the interface shape in a "sc…
The equilibrium shape of liquid drops on elastic substrates is determined by minimising elastic and capillary free energies, focusing on thick incompressible substrates. The problem is governed by three length scales: the size of the drop $R$, the molecular size $a$, and the ratio of surface tension to elastic modulus $γ/E$. We show that the contact angles undergo two transitions upon changing the substrates from rigid to soft. The microscopic wetting angles deviate from Young's law when $γ/Ea \gg 1$, while the apparent macroscopic angle only changes in the very soft limit $γ/ER \gg 1$. The el…
Droplets on hydrophobic surfaces are ubiquitous in microfluidic applications and there exists a number of commonly used multicomponent and multiphase lattice Boltzmann schemes to study such systems. In this paper we focus on a popular implementation of a multicomponent model as introduced by Shan and Chen. Here, interactions between different components are implemented as repulsive forces whose strength is determined by model parameters. In this paper we present simulations of a droplet on a hydrophobic surface. We investigate the dependence of the contact angle on the simulation parameters an…
We study surface nanobubbles using molecular dynamics simulation of ternary (gas, liquid, solid) systems of Lennard-Jones fluids. They form for sufficiently low gas solubility in the liquid, i.e., for large relative gas concentration. For strong enough gas-solid attraction, the surface nanobubble is sitting on a gas layer, which forms in between the liquid and the solid. This gas layer is the reason for the universality of the contact angle, which we calculate from the microscopic parameters. Under the present equilibrium conditions the nanobubbles dissolve within less of a microsecond, consis…
With aim of finding mathematical criteria for contact line depinning from sharp corners, we have studied the equilibrium and stability of a semi-infinite planar liquid layer pinned at the vertex of a wedge. Equilibrium is compatible with a fan of apparent contact angles $θ_0$ bracketed by the equilibrium contact angles of both flanks of the wedge, so the contact line could remain pinned if $θ_0$ is within this fan. However, the analysis of the stability of these solutions, studied exploiting the variational structure of the problem through turning-point arguments, shows that the equilibrium be…
Electrowetting-on-dielectric (EWOD) is a powerful tool in many droplet-manipulation applications with a notorious weakness caused by contact-angle saturation (CAS), a phenomenon limiting the equilibrium contact angle of an EWOD-actuated droplet at high applied voltage. In this paper, we study the spreading behaviours of droplets on EWOD substrates with the range of applied voltage exceeding the saturation limit. We experimentally find that at the initial stage of spreading, the driving force at the contact line still follows the Young-Lippmann law even if the applied voltage is higher than the…
Electrowetting (EW) of water drops in ambient oil has found a wide range of applications including lab-on-a-chip devices, display screens, and variable focus lenses. The efficacy of all these applications is dependent on the contact angle hysteresis (CAH), which is generally reduced in the presence of ambient oil due to thin lubrication layers. While it is well-known that AC voltage reduces the effective contact angle hysteresis (CAH) for EW in ambient air, we demonstrate here that CAH for EW in ambient oil increases with increasing AC and DC voltage. Taking into account the disjoining pressur…
