Reentrant wetting transition on surfactant solution surfaces

The wetting of polydimethylsiloxane oil drops on the surfaces of anionic surfactant sodium dodecylsulfate solutions is studied systematically by changing the bulk surfactant concentration. The wetting state changes from complete wetting to pseudopartial wetting at 0.3 cmc (critical micelle concentration) surfactant concentration and there is a reentrant transition back to complete wetting at 1.4 cmc. The measured free energy is consistent with the prediction of the wetting theory. The interaction potential minimum of the two surfaces of the oil film disappears at the reentrant point, which is speculated to be an effect of micelle formation in the solution.     

Mean-field density-functional model of a second-order wetting transition

First- and second-order wetting transitions are contrasted. A mean-field density-functional model that leads to a second-order transition is introduced. The way in which it differs from an earlier, otherwise similar model in which the transition is first order is noted. The interfacial and line tensions in the model are obtained numerically and their behavior on approach to the transition is determined. The spatial variation of the model's densities in the neighborhood of the contact line near the wetting transition is also found and seen to be characteristically different at a second-order transition from what it is at a first-order transition. The results for the line tension and for the spatial variation of the densities are in accord with those from an earlier interface-displacement model of the same phenomena.     

UVO-tunable superhydrophobic to superhydrophilic wetting transition on biomimetic nanostructured surfaces

A novel strategy for a tunable sigmoidal wetting transition from superhydrophobicity to superhydrophilicity on a continuous nanostructured hybrid film via gradient UV-ozone (UVO) exposure is presented. Along a single wetting gradient surface (40 mm), we could visualize the superhydrophobic (thetaH2O > 165 degrees and low contact angle hysteresis) transition (165 degrees > thetaH2O > 10 degrees ) and superhydrophilic (thetaH2O < 10 degrees within 1 s) regions simply through the optical images of water droplets on the surface. The film is prepared through layer-by-layer assembly of negatively charged silica nanoparticles (11 nm) and positively charged poly(allylamine hydrochloride) with an initial deposition in a fractal manner. The extraordinary wetting transition on chemically modified nanoparticle layered surfaces with submicrometer- to micrometer-scale pores represents a competition between the chemical wettability and hierarchical roughness of surfaces as often occurs in nature (e.g., lotus leaves, insect wings, etc).     

Line and boundary tensions on approach to the wetting transition

A mean-field density-functional model often used in the past in the study of line and boundary tensions at wetting and prewetting transitions is reanalyzed by extensive numerical calculations, approaching the wetting transition much more closely than had previously been possible. The results are what are now believed to be definitive for the model. They include strong numerical evidence for the presence of the logarithmic factors predicted by theory both in the mode of approach of the prewetting line to the triple-point line at the point of the first-order wetting transition and in the line tension itself on approach to that point. It is also demonstrated with convincing numerical precision that the boundary tension on the prewetting line and the line tension on the triple-point line have a common limiting value at the wetting transition, again as predicted by theory. As a by product of the calculations, in the model's symmetric three-phase state, far from wetting, it is found that certain properties of the model's line tension and densities are almost surely given by simple numbers arising from the symmetries, but proving that these are exact for the model remains a challenge to analytical theory.     

Droplets wetting on filament rails: Surface energy and morphology transition

The morphology of liquid droplets wetting on filaments depends on the filament configuration, droplet volume, and contact angle. A stable morphology is the one that minimizes the potential energy of the droplet–filament system, while morphology transition may happen when an intermediate state exists which corresponds to a higher potential energy. This paper aims to explore such morphology transition of droplet wetting on filament rails made of two parallel identical microfilaments. Detailed numerical simulations were performed to extract the surface energy of the droplet–filament system at varying filament spacings, droplet volumes, and contact angles. Critical conditions of the morphology transition between two symmetrical wetting morphologies (i.e., liquid droplet bridge and barrel-shaped droplet) were determined. A family of characteristic curves in terms of the dimensionless droplet volume vs the filament spacing at varying contact angles was obtained, which can be used as a universal law to govern the morphology transition for such droplet–filament rail systems. The results and concepts presented in this work can be extended to broad wetting systems and utilized for the analysis and design of microfluidic devices and testers based on droplet–filament systems.     

Freezing transition of wetting film of tetradecane on tetradecyltrimethylammonium bromide solutions

We have performed ellipsometry and surface tensiometry at tetradecyltrimethylammonium bromide (TTAB) aqueous solution surface coexisting with tetradecane lens as a function of the molality of TTAB and the temperature under atmospheric pressure. From the theoretical analysis of the coefficient of ellipticity, it was clarified that the liquid monolayer comprising the surfactant and alkane is formed at higher surfactant concentrations by the wetting transition of tetradecane lens on the aqueous solution, and the solid monolayer is formed by lowering temperature (freezing transition). The results of the surface tension measurement support the occurrence of wetting transition and the freezing transition. A phase diagram of the wetting film was constructed by ellipsometry and surface tensiometry, of which the mixed solid monolayer had never been reported before. From the thermodynamic analysis of the phase diagram, it is also demonstrated that the TTAB surface density decreases accompanied with the freezing transition, which agrees with surface densities of TTAB calculated from surface tension vs. concentration curves.     

Lattice model for the wetting transition of alkanes on aqueous surfactant solutions

Droplets of alkanes on aqueous solutions of the cationic surfactants C(n)TAB (CH3(CH2)(n-1)N+ (CH3)3Br-) exhibit a first-order wetting transition as the concentration of the surfactant is increased. A theoretical model is presented in which the surface free energy is broken down into a long-range dispersion interaction and a short-range interaction described by a 2D lattice gas, taking into account the interaction between oil and surfactant molecules. The model provides quantitative agreement with the observed wetting transitions and the variation in composition of the wetting film with bulk surfactant concentration. The behavior of oil drops on large reservoirs of dilute surfactant is discussed.     

Resonance Cassie-Wenzel wetting transition for horizontally vibrated drops deposited on a rough surface

The transition between the Cassie and Wenzel wetting regimes has been observed under horizontal vibrations of a water drop placed on the rough micrometrically scaled polymer pattern. The observed transition has a distinct resonance character. The resonance frequencies as established experimentally coincide with the calculated eigenfrequencies of capillary-gravity standing waves on the drop surface. The resonance Cassie-Wenzel transition is related to the displacement of the triple line caused by both the inertia force and the increase in the Laplace pressure. This strengthens the idea that the Cassie-Wenzel wetting transition is most likely a 1D affair stipulated by the triple-line behavior. The study of the vibrated drop deposited on the rough surface supplied valuable information concerning the Cassie-Wenzel wetting transition.     

Short chains at solid surfaces: wetting transition from a density functional approach

A microscopic density functional theory is used to investigate the adsorption of short chains on attractive solid surfaces. We analyze the structure of the adsorbed fluid and investigate how the wetting transition changes with the change of the chain length and with the relative strength of the fluid-solid interaction. End segments adsorb preferentially in the first adsorbed layer whereas the concentration of the middle segments is enhanced in the second layer. We observe that the wetting temperature rescaled by the bulk critical temperature decreases with an increase of the chain length. For longer chains this temperature reaches a plateau. For the surface critical temperature an inverse effect is observed, i.e., the surface critical temperature increases with the chain length and then attains a plateau. These findings may serve as a quick estimate of the wetting and surface critical temperatures for fluids of longer chain lengths.     

Water wetting transition parameters of perfluorinated substrates with periodically distributed flat-top microscale obstacles

Superhydrophobicity is obtained on photolithographically structured silicon surfaces consisting of flat-top pillars after a perfluorosilanization treatment. Systematic static contact angle measurements were carried out on these surfaces as a function of pillar parameters that geometrically determine the surface roughness, including pillar height, diameter, top perimeter, overall filling factor, and disposition. In line with thermodynamics models, two regimes of static contact angles are observed varying each parameter independently: the "Cassie" regime, in which the water drop sits suspended on top of the pillars (referred to as composite), corresponding to experimental contact angles greater than 140-150 degrees, and the "Wenzel" regime, in which water completely wets the asperities (referred to as wetted), corresponding to lower experimental contact angles. A transition between the Cassie and Wenzel regimes corresponds to a set of well-defined parameters. By smoothly depositing water drops on the surfaces, this transition is observed for surface parameter values far from the calculated ones for the thermodynamic transition, therefore offering evidence for the existence of metastable composite states. For all studied parameters, the position of the experimental transition correlates well with a rough estimation of the energy barrier to be overcome from a composite metastable state in order to reach the thermodynamically favored Wenzel state. This energy barrier is estimated as the surface energy variation between the Cassie state and the hypothetical composite state with complete filling of the surface asperities by water, keeping the contact angle constant.     

Effects of hydraulic pressure on the stability and transition of wetting modes of superhydrophobic surfaces

The underlying mechanisms of stability, metastability, or instability of the Cassie-Baxter and Wenzel wetting modes and their transitions on superhydrophobic surfaces decorated with periodic micropillars are quantitatively studied in this article. Hydraulic pressure, which may be generated by the water-air interfacial tension of water droplets or external factors such as raining impact, is shown to be a key to understanding these mechanisms. A detailed transition process driven by increasing hydraulic pressure is numerically simulated. The maximum sustainable or critical pressure of the Cassie-Baxter wetting state on a pillarlike microstructural surface is formulated for the first time in a simple, unified, and precise form. This analytic result reveals the fact that reducing the microstructural scales (e.g., the pillars' diameters and spacing) is probably the most efficient measure needed to enlarge the critical pressure significantly. We also introduce a dimensionless parameter, the pillar slenderness ratio, to characterize the stability of either the Cassie-Baxter or the Wenzel wetting state and show that the energy barrier for transitioning from the Cassie-Baxter to the Wenzel wetting mode is proportional to both the slenderness ratio and the area fraction. Thus, the Cassie-Baxter wetting mode may collapse under a hydraulic pressure lower than the critical one if the slenderness ratio is improperly small. This quantitative study explains fairly well some experimental observations of contact angles that can be modeled by neither Wenzel nor Cassie-Baxter contact angles and eventually leads to our proposals for a mixed (or coexisting) wetting mode.     

Adsorption of polymers on a brush: Tuning the order of the wetting phase transition

We develop a computational methodology for the direct measurement of a wetting transition and its order via the effective interface potential. The method also allows to estimate contact angles in the nonwet state and to study adsorption isotherms. The proposed methodology is employed in order to study the wetting behavior of polymers on top of a brush consisting of identical polymers. In the absence of long-range forces, the system shows a sequence of nonwet, wet, and nonwet states as the brush density is increased. Including attractive long-range interactions we can make the polymer liquid wet the bush at all grafting densities, and both first- and second-order wetting transitions are observed. The latter case is limited to a small interval of grafting densities where the melt wets the brush in the absence of long-range interactions. Second-order wetting transitions are preceded by a first-order surface transition from a thin to a thick adsorbed layer. The interval of second-order wetting transitions is limited at low grafting densities by a surface critical end point and at high grafting densities by a tricritical wetting point. Our study highlights the rich wetting behavior that results when competing adsorbent-substrate interactions of different scales are tuned over a broad range.     

Molecular simulations of wetting of a rough surface by an oily fluid: effect of topology, chemistry, and droplet size on wetting transition rates

The goal of this work is to study via molecular simulations the wetting kinetics of a rough surface by an oily fluid. We use forward flux sampling to compute the wetting transition rate and elucidate the transition mechanism of a small droplet on a surface of nails. The nails provide the re-entrant geometry necessary to keep the droplet in the nonwetted, composite state. The effects of nail height, droplet size, and surface chemistry are investigated. Because the droplet must touch the bottom surface to transition, increasing the nail height is an effective way to increase the barrier to wetting for both phobic and slightly philic drops, although as the fluid becomes very philic, chemistry dominates and the effect of nail height disappears. Generally, smaller drops transition more easily. Overall, our results suggest that nonwettability could be practically enhanced by promoting the "kinetic" trapping of the system in the nonwetted state.     

Enantiospecific wetting

Experiments have shown that enantiospecificity can be important in wetting. Measurements of droplet contact angles can be used to estimate the energy of enantiomeric discrimination.     

Surface wetting in liquid-liquid-solid triphase systems: solid-phase-independent transition at the liquid-liquid interface by lewis Acid-base interactions

Interfacial phenomena: A solid-phase-independent strategy for tuning the surface wettability is presented. Lewis acid-base interactions at the oil-water interface can greatly decrease the liquid-liquid interfacial tension and induce oleophilic to superoleophobic wetting transition on a nonresponsive microstructured surface.     

Dynamics of wetting

We review the mechanisms controlling the dynamics of wetting in partial and complete wetting regimes. It is shown that the behaviour in several timescales may characterize the dynamics since different channels of energy dissipation have to be considered within spreading.     

Spreading of completely wetting or partially wetting power-law fluid on solid surface

This study investigated the drop-spreading dynamics of pseudo-plastic and dilatant fluids. Experimental results indicated that the spreading law for both fluids is related to rheological characteristics or power exponent n. For the completely wetting system, the evolution of the wetting radius over time can be expressed by the power law R = atm, where the spreading exponent m of the dilatant fluids is >0.1 and the spreading exponent m of pseudo-plastic fluids is <0.1. The strength of non-Newtonian effects is positively correlated to the extent of deviation from the theoretical value 0.1 of m for Newtonian fluids. For the partially wetting system, the power law on the time dependence of the wetting radius no longer holds; therefore, an exponential power law, R = Req(1-exp(-at(m)/Req)), is proposed, where Req denotes the equilibrium radius of drop and a is a coefficient. Comparing experimental data with the exponential power law revealed that both are in good agreement.     

Dynamics of partial wetting

Two broad classes of models have been used to describe the motion of a contact line when the contact angle θ deviates from the equilibrium value θ_e : a) an Eyring approach, emphasizing the microscopic jump of a single molecule at the tip. b) a hydrodynamic approach, concentrating on the viscous losses inside the liquid wedge of angle θ. In the present review, we compare the predictions from both models, for two critical experiments: 1) The pull out of a vertical plate from a fluid at rest -showing (for finite θ_e) a critical velocity V_c above which the plate is completely wet. 2) The velocity of growth of a dry patch for a non wettable surface covered by a flat liquid film -which turns out to vary like θ_e³ at small θ_e.The net conclusion is that, at small θ_e and for low velocities V, the hydrodynamic losses dominate, while at large θ_e and large V, the molecular features are probably important.