We extend the Cahn-Landau-de Gennes mean field theory of binary mixtures to understand the wetting thermodynamics of a three phase system, that is in contact with an external surface which prefers one of the phases. We model the system using a phenomenological free energy having three minima corresponding to low, intermediate and high density phases. By systematically varying the \textit{(i)} depth of the central minimum, \textit{(ii)} the surface interaction parameters, we explore the phase behavior, and wetting characteristics of the system across the triple point corresponding to three phase coexistence. We observe a non-monotonic dependence of the surface tension across the triple point that is associated with a complete to partial wetting transition. The methodology is then applied to study the wetting behaviour of a polymer-liquid crystal mixture in contact with a surface using a renormalised free energy. Our work provides a way to interrogate phase behavior and wetting transitions of biopolymers in cellular environments.
We investigated a possibility of application of liquid metal contacts for devices based on thermotunneling. Electric and thermal characteristics of low wetting contact Hg/Si, and high wetting contacts Hg/Cu were determined and compared. We got tunneling I-V characteristics for Hg/Si, while for Hg/Cu, I-V characteristics were ohmic. We explained tunneling I-V characteristics by presence of nanogap between the contact materials. Heat conductance of high wetting and low wetting contacts were compared, using calorimeter measurements. Heat conductance of high wetting contact was 3-4 times more than…
Hypothesis: Although wetting agents have been developed to limit tear film dewetting over contact lenses, systematic analyses correlating wetting agents properties to mechanisms of the tear film destabilization are not readily available. Clarifying destabilization characteristics across key physio-chemical variables will provide a rational basis for identifying optimal wetting agents. Experiments: We employ an in-house, in vitro platform to comprehensively evaluate drainage and dewetting dynamics of five wetting agents across seventeen different formulations and two model tear film solutions: …
A partially-wetting liquid can deform the underlying elastic substrate upon which it rests. This situation requires the development of theoretical models to describe the wetting forces imparted by the drop onto the solid substrate, particularly those at the contact-line. We construct a general solution using a displacement potential function for the elastic deformations within a finite elastic substrate associated with these wetting forces, and compare the results for several different contact-line models. Our work incorporates internal contributions to the surface stress from both liquid/soli…
We introduce an accurate and efficient method for characterizing surface wetting and interfacial properties, such as the contact angle made by a liquid droplet on a solid surface, and the vapor-liquid surface tension of a fluid. The method makes use of molecular simulations in conjunction with the indirect umbrella sampling technique to systematically wet the surface and estimate the corresponding free energy. To illustrate the method, we study the wetting of a family of Lennard-Jones surfaces by water. We estimate contact angles for surfaces with a wide range of attractions for water by using…
We discuss an evaporation-induced wetting transition on superhydrophobic stripes, and show that depending on the elastic energy of the deformed contact line, which determines the value of an instantaneous effective contact angle, two different scenarios occur. For relatively dilute stripes the receding angle is above 90$^\circ$, and the sudden impalement transition happens due to an increase of a curvature of an evaporating drop. For dense stripes the slow impregnation transition commences when the effective angle reaches 90$^\circ$ and represents the impregnation of the grooves from the tripl…
We consider a nano-patterned planar wall consisting of a periodic array of stripes of width $L$, which are completely wet by liquid (contact angle $θ=0$), separated by regions of width $D$ which are completely dry (contact angle $θ=π)$. Using microscopic Density Functional Theory we show that in the presence of long-ranged dispersion forces, the wall-gas interface undergoes a first-order wetting transition, at bulk coexistence, as the separation $D$ is reduced to a value $D_w\propto\ln L$, induced by the bridging between neighboring liquid droplets. Associated with this is a line of pre-wettin…
Ferrofluids are liquids exhibiting remarkably strong response to magnetic fields, which leads to fascinating properties useful in various applications. Understanding the wetting properties and spreading of ferrofluids is important for their use in microfluidics and magnetic actuation. However, this is challenging as magnetically induced deformation of the ferrofluid surface can affect contact angles, which are commonly used to characterize wetting properties in other systems. In addition, interaction of the magnetic nanoparticles and solid surface at nanoscale can have surprising effects on fe…
For over 200 years, wettability has made significant contributions to understanding the properties of objects, advancing technological progress. Theoretical model of the contact angle (CA) for evaluating wettability has constantly been modified to address relevant emerging issues. However, these existing models disregard the difference in the CA along the contact line and use a single-point CA to evaluate the entire contact line. From this perspective, there is no reasonable explanation for noncircular wetting. Here, we reveal that noncircular wetting boundaries result from property difference…
Controlling the spatial distribution of liquid droplets on surfaces via surface energy patterning can be used to control material delivery to specified regions via selective liquid/solid wetting. While studies of the equilibrium shape of liquid droplets on heterogenous substrates exist, much less is known about the corresponding wetting kinetics. We make significant progress towards elucidating details of this topic by studying, via large-scale atomistic simulations, liquid nanodroplets spreading on chemically patterned surfaces. A model is presented for lines of polymer liquid (droplets) on s…
A lattice model for active matter is studied numerically, showing that it displays wettings transitions between three distinctive phases when in contact with an impenetrable wall. The particles in the model move persistently, tumbling with a small rate $α$, and interact via exclusion volume only. When increasing the tumbling rates $α$, the system transits from total wetting to partial wetting and unwetting phases. In the first phase, a wetting film covers the wall, with increasing heights when $α$ is reduced. The second phase is characterized by wetting droplets on the wall with a periodic spa…
The behavior of weakly deformed drops on non wetting surfaces is usually described using linear models. We show that these simple pictures cannot account for measurements of the dynamics of droplets that oscillate or bounce on super-hydrophobic substrates. We demonstrate that several peculiar experimental observations observed in previous works can be understood through a logarithmic correction of the linear model.
We study the dynamics of contact angle of a droplet of binary solution evaporating on a super wetting surface. Recent experiments show that although equilibrium contact angle of such droplet is zero, the contract angle can show complex time dependence before reaching the equilibrium value. We analyse such phenomena by extending our previous theory for the dynamics of an evaporating single component droplet to double component droplet. We show that the time dependence of the contact angle can be quite complex. Typically, it first decreases slightly, and then increases and finally decreases agai…
We report on the onset of fluid entrainment when a contact line is forced to advance over a dry solid of arbitrary wettability. We show that entrainment occurs at a critical advancing speed beyond which the balance between capillary, viscous and contact line forces sustaining the shape of the interface is no longer satisfied. Wetting couples to the hydrodynamics by setting both the morphology of the interface at small scales and the viscous friction of the front. We find that the critical deformation that the interface can sustain is controlled by the friction at the contact line and the visco…
The relation between the contact angle of a liquid drop and the morphological parameters of self-affine solid surfaces have been investigated. We show experimentally that the wetting property of a solid surface crucially depends on the surface morphological parameters such as: (1) root mean square (rms) roughness $σ$, (2) in-plane roughness correlation length $ξ$ and (3) roughness exponent $α$ of the self-affine surface. We have shown that the contact angle monotonically decreases with the increase in the rms local surface slope $ρ$ ($\propto σ/ξ^α$) for the cases where the liquid wets the cre…
The capillary traction of a liquid contact line causes highly localized deformations in soft solids, tremendously slowing down wetting and dewetting dynamics by viscoelastic braking. Enforcing nonetheless large velocities leads to the so-called stick-slip instability, during which the contact line periodically depins from its own wetting ridge. The mechanism of this periodic motion and, especially, the role of the dynamics in the fluid have remained elusive, partly because a theoretical description of the unsteady soft wetting problem is not available so far. Here we present the first numerica…
An analytical model is proposed for the Young-Laplace equation of two-dimensional (2D) drops under gravity. Inspired by the pioneering work of Landau & Lifshitz (1987), we derive analytical expressions of the profile of drops on flat surfaces, for arbitrary contact angles and drop volume. We then extend our theory for drops on inclined surfaces and reveal that the contact line plays a key role on the wetting state of the drops: (1) when the contact line is completely pinning, the advancing and receding contact angles and the shape of the drop can be uniquely determined by the predefined drople…
The electrostatic interaction between pairs of spherical or macroscopically long, parallel cylindrical colloids trapped at fluid interfaces is studied theoretically for the case of small inter-particle separations. Starting from the effective interaction between two planar walls and by using the Derjaguin approximation, we address the issue of how the electrostatic interaction between such particles is influenced by their curvatures and by the wetting contact angle at their surfaces. Regarding the influence of curvature, our findings suggest that the discrepancies between linear and nonlinear …
We investigate critical wetting transitions for fluids adsorbed in wedge-like geometries where the substrate height varies as a power-law, $z(x,y) \sim |x| ^γ$, in one direction. As $γ$ is increased from 0 to 1, the substrate shape is smoothly changed from a planar-wall to a linear wedge. The continuous wetting and filling transitions pertinent to these limiting geometries are known to have distinct phase boundaries and critical singularities. We predict that the intermediate critical wetting behaviour occurring for $0<γ< 1$ falls into one of {\it{three}} possible regimes depending on the valu…
Wetting of sessile bubbles on solid and liquid surfaces has been studied. A model is presented for the contact angle of a sessile bubble based on a modified Young equation - the experimental results agree with the model. A hydrophilic surface results in a bubble contact angle of 90 deg whereas on a superhydrophobic surface one observes 134 deg. For hydrophilic surfaces, the bubble angle diminishes with bubble radius - whereas on a superhydrophobic surface, the bubble angle increases. The size of the Plateau borders governs the bubble contact angle - depending on the wetting of the surface.
The size-dependent contact angle and the drying and wetting morphological transition are studied with respect to the volume change for a spherical cap-shaped droplet placed on a spherical substrate. The line-tension effect is included using the rigorous formula for the Helmholtz free energy in the droplet capillary model. A morphological drying transition from a cap-shaped to a spherical droplet occurs when the substrate is hydrophobic and the droplet volume is small, similar to the transition predicted on a flat substrate. In addition, a morphological wetting transition from a cap-shaped to a…
The dynamics of the triple gas-liquid-solid contact line is analysed for the case where the gas is the saturated vapour corresponding to the liquid, like in the vapour bubble in boiling. It is shown that even small superheating (with respect to the saturation temperature) causes evaporation of the adsorption liquid film and the true triple contact is established. It is shown that the hydrodynamic contact line singularity cannot be relaxed with the Navier slip condition under such circumstances. Augmented with the second derivative slip condition is proposed to be applied. For the partial wetti…
Four on-lattice and six off-lattice models for active matter are studied numerically, showing that in contact with a wall, they display universal wetting transitions between three distinctive phases. The particles, which interact via exclusion volume only, move persistently and, depending on the model, change their direction either via tumble processes or rotational diffusion. When increasing the turning rate $ν_T$, the systems transit from total wetting, to partial wetting and dewetted phases. In the first phase, a wetting film covers the wall, with increasing heights while decreasing $ν_T$. …
The fundamental impacts of surface geometry on the stability of wetting states, and the transitions between them are elucidated for posts and reentrant structures in both two and three dimensions. We identify three principal outcomes of particular importance for future surface design of liquid-repellent surfaces. Firstly, we demonstrate and quantify how capillary condensation and vapour cavitation affect wetting state stabilities, and the roles condensates play in wetting transitions. Crucially, this leads to a description of the surface structures which exhibit a suspended state in the absenc…
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…
The spreading of liquid drops on soft substrates is extremely slow, owing to strong viscoelastic dissipation inside the solid. A detailed understanding of the spreading dynamics has remained elusive, partly owing to the difficulty in quantifying the strong viscoelastic deformations below the contact line that determine the shape of moving wetting ridges. Here we present direct experimental visualisations of the dynamic wetting ridge, complemented with measurements of the liquid contact angle. It is observed that the wetting ridge exhibits a rotation that follows exactly the dynamic liquid cont…
Osmotic deflation of vesicles enclosing two liquid phases can lead to bulging of one of the phases from the vesicle body. This budding process is preceded by a complete to partial wetting transition of one of the liquid phases on the membrane and depends on the membrane tensions and the tension of the interface between the enclosed liquid phases. These tensions dominate in different morphology regimes, the crossover of which initiates the budding process. In addition, the degree of budding can be controlled by aspiration via micropipettes. We also demonstrate that the budding direction can be …
In the classic theory of solid adhesion, surface energy drives deformation to increase contact area while bulk elasticity opposes it. Recently, solid surface stress has been shown also to play an important role in opposing deformation of soft materials. This suggests that the contact line in soft adhesion should mimic that of a liquid droplet, with a contact angle determined by surface tensions. Consistent with this hypothesis, we observe a contact angle of a soft silicone substrate on rigid silica spheres that depends on the surface functionalization but not the sphere size. However, to satis…
The analytical expressions of liquid-vapor macroscopic contact angles are analyzed for various simple geometries and arrangements of the substrate, in particular when the latter exhibits two or more scales. It concerns the Wenzel state of wetting when the substrate is completely wet, the Cassie-Baxter state when the liquid hangs over the substrate, but also intermediate states of wetting which are shown to be relevant and in competition with the two other ones. Under a separation of scales hypothesis, a composition rule of contact angles is developed whose interest is illustrated in a close pa…
We discuss the effect of an external electric field on the wetting of a solid surface by liquid. To this end, we use a model of the two-level-atom fluid for which the changes in interatomic interactions due to the presence of the field can be found using quantum-mechanical perturbation theory. Constructing the grand potential functional, we perform the standard calculations of Young's equilibrium contact angle. The switching on of the electric field $|{\bf {E}}| > 0$ may increase noticeably the contact angle $θ$.
Real world surfaces can often be modeled as a collection of edges, corners, dents or spikes of varying roundness. These features exhibit individual spontaneous wetting behaviors comprising pinned contact lines, rivulets or cusps. If occurring in proximity to one another, as is often the case in applications, these wetting properties interact, resulting in an overall changed wetting pattern on the surface. Hence, there is considerable interest in understanding when, and to what extent, interactions occur, and how wetting then deviates from the wetting of isolated surface features. The present s…
A mean-field theory is presented which describes the basic observations of recent experiments revealing rich wetting behaviour of n-alkane/methanol mixtures at the liquid-vapour interface. The theory, qualitative and in part heuristic, is based on a microscopic lattice-gas model from which a Cahn-Landau approach is distilled. Besides the physics associated with the short-range components of the intermolecular interactions, effects of the long-range tails of the net van der Waals forces between interfaces are also taken into account. Including weak long-range forces which favour wetting in the …
Using experiments and numerical simulations, we investigate the spontaneous spreading of droplets of aqueous glycerol (Newtonian) and aqueous polymer (shear-thinning) solutions on smooth surfaces. We find that in the first millisecond the spreading of the shear-thinning solutions is identical to the spreading of water, regardless of the polymer concentration. In contrast, aqueous glycerol solutions show a different behavior, namely, significantly slower spreading rate than water. In the initial rapid spreading phase, the dominating forces that can resist the wetting are inertial forces and con…
Liquid-liquid wetting failure is investigated in a two-dimensional Couette system with two immiscible fluids of arbitrary viscosity. The problem is solved exactly using a sharp interface treatment of hydrodynamics (lubrication theory) as a function of the capillary number, viscous ratio and separation of scale, i.e. slip length versus macroscopic scale of the system. The existence of critical velocities, above which no stationary solutions are found, is analyzed in detail in terms of the relevant parameters of the system. Comparisons with existing analysis for other geometries are also carried…
An inkjet printer head, which is capable of depositing liquid droplets with a resolution of $22$ picoliters and high repeatability, is employed to investigate the wetting dynamics of drops printed on a horizontal plane as well as on a granular monolayer. For a sessile drop on a horizontal plane, we characterize the contact angle hysteresis, drop volume and contact line dynamics from side view images. We show that the evaporation rate scales with the dimension of the contact line instead of the surface area of the drop. We demonstrate that the system evolves into a closed cycle upon repeating t…
The wetting properties of multi-component liquids are crucial to numerous industrial applications. The mechanisms that determine the contact angles for such liquids remain poorly understood, with many intricacies arising due to complex physical phenomena, for example due to the presence of surfactants. Here, we consider two-component drops that consist of mixtures of vicinal alkane diols and water. These diols behave surfactant-like in water. However, the contact angles of such mixtures on solid substrates are surprisingly large. We experimentally reveal that the contact angle is determined by…
Due to the slow dynamics of the wetting ridge, it is challenging to predict the wetting morphology of liquid drops on thin lubricant coated surfaces. It is hypothesized that when a drop sinks on a lubricated surface, quasi-static wetting morphology can be numerically computed only from the knowledge of interfacial energies, lubricant thickness, and drop volume. We used Surface Evolver software for the numerical computation of the interface profiles for a four-phase system. For the experiments, we used drops of 80 wt% formamide on silicone oil coated substrates with varying lubricant thickness,…
The electric double layer structure in an electrolyte close to a solid substrate near the three-phase contact line is approximated by considering the linearized Poisson-Boltzmann equation in a wedge geometry. The mathematical approach complements the semi-analytical solutions reported in the literature by providing easily available characteristic information on the double layer structure. In particular, the model contains a length scale that quantifies the distance from the fluid-fluid interface over which this boundary influences the electric double layer. The analysis is based on an approxim…
In forced wetting, a rapidly moving surface drags with it a thin layer of trailing fluid as it is plunged into a second fluid bath. Using high-speed interferometry, we find characteristic structure in the thickness of this layer with multiple thin flat triangular structures separated by much thicker regions. These features, depending on liquid viscosity and penetration velocity, are robust and occur in both wetting and de-wetting geometries. Their presence clearly shows the inadequacy of theoretical analysis that ignores the instability in the transverse direction.
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…
Multi-color Stochastic Rotation Dynamics (SRDmc) has been introduced by Inoue et al. as a particle based simulation method to study the flow of emulsion droplets in non-wetting microchannels. In this work, we extend the multi-color method to also account for different wetting conditions. This is achieved by assigning the color information not only to fluid particles but also to virtual wall particles that are required to enforce proper no-slip boundary conditions. To extend the scope of the original SRDmc algorithm to e.g. immiscible two-phase flow with viscosity contrast we implement an angul…
Microstructured surfaces that control the direction of liquid transport are not only ubiquitous in nature, but they are also central to technological processes such as fog/water harvesting, oil-water separation, and surface lubrication. However, a fundamental understanding of the initial wetting dynamics of liquids spreading on such surfaces is lacking. Here, we show that three regimes govern microstructured surface wetting on short time scales: spread, stick, and contact line leaping. The latter involves establishing a new contact line downstream of the wetting front as the liquid leaps over …
In this article, we study the spreading of droplets of density-matched granular suspensions on the surface of a solid. Bidispersity of the particle size distribution enriches the conclusions drawn from monodisperse experiments by highlighting key elements of the wetting dynamics. In all cases, the relation between the dynamic contact angle and the velocity of the contact line follows a similar relation as that of a simple fluid, despite the complexity introduced by the presence of particles. We extract from this relation an apparent wetting viscosity of the suspensions that differs from that m…
The interaction of interfacial water with graphitic carbon at the atomic scale is studied as a function of the hydrophobicity of epitaxial graphene. High resolution X-ray reflectivity shows that the graphene-water contact angle is controlled by the average graphene thickness, due to the fraction of the film surface expressed as the epitaxial buffer layer whose contact angle (contact angle θ_c = 73°) is substantially smaller than that of multilayer graphene (θ_c = 93°). Classical and ab initio molecular dynamics simulations show that the reduced contact angle of the buffer layer is due to both …
The effect of thermal fluctuations near a contact line of a liquid interface partially wetting an impenetrable substrate is studied analytically and numerically. Promoting both the interface profile and the contact line position to random variables, we explore the equilibrium properties of the corresponding fluctuating contact line problem based on an interfacial Hamiltonian involving a "contact" binding potential. To facilitate an analytical treatment we consider the case of a one-dimensional interface. The effective boundary condition at the contact line is determined by a dimensionless para…
The influence of the external pressure and surface energy on the wetting transition at nanotextured interfaces is studied using molecular dynamics and continuum simulations. The surface roughness of the composite interface is introduced via an array of spherical nanoparticles with controlled wettability. We find that in the absence of an external pressure, the liquid interface is flat and its location relative to the solid substrate is determined by the particle size and the local contact angle. With increasing pressure on the liquid film, the interface becomes more curved and the three-phase …
Phase transformations such as freezing typically start with heterogeneous nucleation. Heterogeneous nucleation near a wetting transition, of a crystalline phase is studied. The wetting transition occurs at or near a vapour-liquid transition which occurs in a metastable fluid. The fluid is metastable with respect to crystallisation, and it is the crystallisation of this fluid phase that we are interested in. At a wetting transition a thick layer of a liquid phase forms at a surface in contact with the vapour phase. The crystalline nucleus is then immersed in this liquid layer, which reduces the…
We present results showing how water drops, produced by ink-jet printing, spread on surfaces patterned with lattices of diamond or triangular posts. Considering post widths typically ~7 m and lattice spacings between 15-40 m, we observe drop shapes with 3,4 and 6-fold symmetry, depending on both the symmetry of the lattice and the shape of the posts. This is a result of the different mechanisms of interface pinning and depinning which depend on the direction of the contact line motion with respect to the post shape. Lattice Boltzmann simulations are used to describe these mechanisms in detail …
There is a huge interest in developing super-repellent surfaces for anti-fouling and heat transfer applications. To characterize the wetting properties of such surfaces, the most common approach is to place a millimetric-sized droplet and measure its contact angles. The adhesion and friction forces can then be indirectly inferred from the Furmidge's relation. While easy to implement, contact angle measurements are semi-quantitative and cannot resolve wetting variations on a surface. Here, we attach a micrometric-sized droplet to an Atomic Force Microscope cantilever to directly measure adhesio…
Young's law fails on soft solid and liquid substrates where there are substantial deformations near the contact line. On liquid substrates, this is captured by Neumann's classic analysis, which provides a geometrical construction for minimising the interfacial free energy. On soft solids, the total free energy includes an additional contribution from elasticity. A linear-elastic model incorporating an out-of-plane restoring force due to solid surface tension was recently shown to accurately predict the equilibrium shape of a thin elastic film due to a large sessile droplet. Here, we extend thi…
Wetting and drying phenomena are studied for flexible and semiflexible polymer solutions via coarse-grained molecular dynamics simulations and density functional theory calculations. The study is based on the use of Young's equation for the contact angle, determining all relevant surface tensions from the anisotropy of the pressure tensor. The solvent quality (or effective temperature, equivalently) is varied systematically, while all other interactions remain unaltered. For flexible polymers, the wetting transition temperature $T_{\rm w}$ increases monotonically with chain length $N$, while t…
