Sliding of water droplets on hydrophobic surfaces with various hydrophilic region sizes

Four patterned surfaces with hydrophilic areas of different sizes were prepared using photolithography with a smooth octadecyltrimethoxysilane (ODS) hydrophobic coating. The hydrophilic area in the surfaces was aligned hexagonally with a constant area fraction. The sliding angle and contact angle hysteresis of the water droplets increased concomitantly with increasing pattern size. The increase of the contact line distortion between defects at the receding side plays an important role in this trend. The droplet sliding velocity also increased concomitantly with increasing pattern size. This trend was simulated by a simple flow model. The contribution of the interface between the ODS region and the hydrophilic area was deduced from this trend. This study demonstrated the different size dependency of the chemical surface defects for sliding behavior between the critical moment at which a droplet slides down and the period when a droplet is sliding.     

Sliding behavior of water droplets on flat polymer surface

Flat films of methyl methacrylate-fluoroalkyl methacrylate copolymers were prepared, and their hydrophobicity was investigated. It was revealed that the F concentration directly affects the static hydrophobicity on the flat polymer surface in a systematic manner. Furthermore, the sliding behavior of a water droplet on these surfaces depends on the static hydrophobicity; the sliding motion changes from constant velocity to constant acceleration with an increase in the water contact angle.     

Displacement of liquid droplets on a surface by a shearing air flow

The motion of droplets on surfaces is crucial to the performance of a wide range of processes; this study examines the initiation of droplet motion through a shearing mechanism generated here by a controlled air flow. Systematic experiments are carried out for a range of fluids and well defined surfaces. A model is postulated that balances surface tension forces at the contact line and the drag force due to the air motion. Experiments reveal that the critical velocity at which droplet motion is initiated depends on the contact angle and the droplet size. Visualizations highlight three modes of motion: (I) the droplet retains a footprint similar to that at the point of motion; (II) a tail exists at the rear of the droplet; (III) a trail remains behind the droplet (that can shed smaller droplets). The predictions of droplet initiation velocity are good for type I motion, in accordance with the assumptions inherent within the model. This model confirms the dominant physics associated with the initiation of droplet motion and provides a useful predictive expression.     

Factors controlling the formation and stability of air bubbles stabilized by partially hydrophobic silica nanoparticles

Air bubbles have been formed using partially hydrophobic silica nanoparticles as the stabilizer. The particles were of primary particle size 20 nm, chemically treated to different degrees with dichlorodimethylsilane to render them partially hydrophobic. Above a certain bubble size range (typically 80-microm diameter), the bubbles seemed to be almost indefinitely stable, while for any size above 20 microm their stability against disproportionation is far better than bubbles stabilized by any protein film investigated in previous studies. A possible theoretical justification for this observation is presented. Bubbles could be formed by shaking water with the particles, but a much higher volume fraction of bubbles was obtained by pressurizing the aqueous phase to 5 atm overnight followed by suddenly releasing the pressure to nucleate bubbles within the silica dispersion. Sonicating the silica dispersion before nucleation also gave more bubbles, which were also found to be more stable. There appeared to be an optimum degree of surface hydrophobicity that gave maximum foamability and foam stability, where around 20-33% of the silanol groups on the silica surface had been converted to dimethylsilane groups. However, a sharp increase in stability occurred when between 1.8 and 2 mol dm(-3) NaCl was also included in the aqueous phase. The change in stability due to inclusion of salt can be rationalized in terms of changes occurring in the value of the particle contact angle. The effects of increasing sonication and an optimum surface chemical treatment can be explained by the need to make the particles sufficiently hydrophobic so that they adsorb strongly enough, while at the same time minimizing their tendency to aggregate in the bulk aqueous phase, which hinders their adsorption. Furthermore, confocal laser scanning microscopy of the bubble dispersions suggests that a large volume fraction of stable bubbles is only formed when the particles adsorbed to the bubbles are also part of a spanning silica particle network in the bulk aqueous solution, forming a weak gel with a finite yield stress.     

Crystallization of condensation droplets on a liquid surface

Highly ordered microporous two-dimensional membranes have been obtained from polymer solutions (Widawski et al. (1994) Nature 369: 397–399). Recently, a mechanism for the formation of such membranes was proposed, involving water vapour condensation (induced by the rapid evaporation of the volatile solvent) onto the surface of solutions and the formation of floating water droplets. Unfortunately, the droplets growth process was not observed, and consequently only qualitative information was reported. In the present paper, results of light-scattering experiments with this system are reported. The formation of water droplets growing at the surface of the solution has been observed and the evolution with time of the mean droplet radius has been found to be described by a power law with an exponent of 1/3, proving that no coalescence processes occur. This particular behaviour is attributed to the precipitation of the polymer at the water/solution interface and to the formation of a mechanically resistant polymer layer encapsulating each droplet. In this way, water droplets behave like solid particles, allowing compact sheets to be formed. The presence of important surface currents is believed to promote the formation of “polycrystal” and “monocrystal” patterns. Received: 4 January 1999 Accepted in revised form: 15 February 1999     

Sliding behavior of liquid droplets on tilted Langmuir-Blodgett surfaces

The sliding behavior of liquid droplets on inclined Langmuir-Blodgett surfaces was investigated. The critical sliding angle defined as the tilt angle of the surface at which the drop slides down as well as the advancing and receding contact angles was measured for five different liquids on five surfaces. In addition, the contact line geometry was analyzed at critical sliding angle. The experimental relationship between the surface tension forces resulting from contact angle hysteresis and the weight of the drop was compared to theoretical predictions. Even though the shape of the drop bases was found as skewed ellipses, a model assuming parallel-sided elongated drops is shown to describe reasonably the experimental values. This result probably indicates the main influence of the capillary forces at the rear and front edges of the drop with respect to that exerted on the lateral sides.     

Formation of droplets and bubbles in a microfluidic T-junction-scaling and mechanism of break-up

This article describes the process of formation of droplets and bubbles in microfluidic T-junction geometries. At low capillary numbers break-up is not dominated by shear stresses: experimental results support the assertion that the dominant contribution to the dynamics of break-up arises from the pressure drop across the emerging droplet or bubble. This pressure drop results from the high resistance to flow of the continuous (carrier) fluid in the thin films that separate the droplet from the walls of the microchannel when the droplet fills almost the entire cross-section of the channel. A simple scaling relation, based on this assertion, predicts the size of droplets and bubbles produced in the T-junctions over a range of rates of flow of the two immiscible phases, the viscosity of the continuous phase, the interfacial tension, and the geometrical dimensions of the device.     

Adsorption of water soluble ionic/hydrophobic diblock copolymer on a hydrophobic surface

Summary We consider the adsorption of aA-B diblock copolymer on a planar hydrophobic surface in aqueous solution. The hydrophobic anchor (A) block is envisioned to avoid water and adsorbs on the solid-liquid interface in a collapsed state. The buoy block (B) is a polyelectrolyte which expands in solution and forms a brush whose structure depends strongly on the ionic strength of the solution. The minimization of the grand canonical free energy of the system gives access to the surface density (), the thickness of the collapsed layer (L _A ) and the thickness of the external polyelectrolyte layer (L _B ). These three parametersL _B ,L _A and are functions of the molecular weight of the anchored block (N _A ), the molecular weight of the buoy block (N _B ), the charge of the polymer (Z) and the ionic strength of the aqueous solution ( _s ).     

Wetting behavior of water droplets on hydrophobic microtextures of comparable size

The wetting behavior of water droplets on periodically structured hydrophobic surfaces was investigated. The effect of structure geometry, roughness, and relative pore fraction on the contact angles was investigated experimentally for droplets of size comparable to the size of the structures. It was found that surface geometry may induce a transition from groove-filling and Wenzel-like behavior to nonfilling of surface grooves and consequential Cassie-Baxter behavior. Numerical calculations of the free energy of these systems suggest that the equilibrium behavior is in line with the experimental observations. The observations may serve as guidelines for the design of surfaces with the desired wetting behavior.     

Formation of viscoelastic protein droplets on a chemically functionalized surface

Droplet formation during adsorption of the protein lactoferrin from an aqueous solution on a surface functionalized by plasma deposited poly(acrylic acid) is studied using quartz crystal microbalance and atomic force microscopy. The formation of protein droplets is particularly favored at pH values close to the isoelectric point of lactoferrin, where the molecules carry little excess charge and intermolecular attraction exceeds the molecule-surface interaction. By combining topographic data with information on the system dynamics, it is possible to describe the viscoelastic properties of the adsorbate within a quantitative model for nonhomogeneous layers.     

Stretching liquid bridges with bubbles: the effect of air bubbles on liquid transfer

Liquid bridges containing bubbles are relevant to industrial printing and are also a topic of fundamental scientific interest. We use flow visualization to study the stretching of liquid bridges, both with and without bubbles, at low capillary numbers. We find that whereas the breakup of wetting fluids between two identical surfaces is symmetric about the bridge midpoint, contact line pinning breaks this symmetry at slow stretching speeds for nonwetting fluids. We exploit this observation to force air bubbles selectively toward the least hydrophilic plate confining the liquid bridge.     

The effect of surface active solutes on bubbles exposed to ultrasound

A review of the effects of a range of surface active solutes, aliphatic alcohols, alkyl amines, carboxylic acids and surfactants on bubbles exposed to ultrasound is presented. The solutes are shown to affect the phenomenon of sonoluminescence (SL) in quite a number of different ways. Ionic surfactants have a strong influence on interbubble interactions which at low concentrations (1 mM) results in an enhancement in SL. Alcohols and the neutral forms of the organic acids and amines induce SL quenching. The SL quenching is attributed to the formation and accumulation of decomposition products in the hot core of an oscillating bubble resulting from the evaporation of volatile solute adsorbed at the bubble interface. Some results are presented on the influence of low concentrations of alcohol on the SL generated from a single bubble and on the bubble dynamics, when exposed to ultrasound. These results add support to the interpretation given for solute-induced effects observed in multibubble systems. It is also shown that SL can be used as an internal light source to excite aromatic solutes that subsequently fluoresce, a process referred to as sonophotoluminescence.     

The spontaneous polarization of a polar liquid close to a hydrophobic surface

The phenomenological vector model is used to discuss parallel orientation and spontaneous polarization of molecular dipole moments of a polar substance close to a hydrophobic surface.     

Physisorption of hydroxide ions from aqueous solution to a hydrophobic surface

We present results from detailed molecular dynamics simulations revealing a counterintuitive spontaneous physical adsorption of hydroxide ions at a water/hydrophobic interface. The driving force for the migration of the hydroxide ions from the aqueous phase is the preferential orientation of the water molecules in the first two water layers away from the hydrophobic surface. This ordering of the water molecules generates an electrical potential gradient that strongly and favorably interacts with the dipole moment of the hydroxide ion. These findings offer a physical mechanism that explains intriguing experimental reports indicating that the interface between water and a nonionic surface is negatively charged.     

Sliding/rolling phobic droplets along a fiber: measurement of interfacial forces

Phobic droplet-fiber systems possess complex geometries, which have made full characterization of such systems difficult. This work has used atomic force microscopy (AFM) to measure droplet-fiber forces for oil droplets on oleophobic fibers over a range of fiber diameters. The work adapted a previous method and a theoretical model developed by the authors for philic droplet-fiber systems. A Bayesian statistical model was also used to account for the influence of surface roughness on the droplet-fiber force. In general, it has been found that the force required to move a liquid droplet along an oleophobic filter fiber will be less than that required to move a droplet along an oleophilic fiber. However, because of the effects of pinning and/or wetting behavior, this difference may be less than would otherwise be expected. Droplets with a greater contact angle (~110°) were observed to roll along the fiber, whereas droplets with a lesser contact angle (<90°) would slide.     

Motion of a drop on a solid surface due to a wettability gradient

The hydrodynamic force experienced by a spherical-cap drop moving on a solid surface is obtained from two approximate analytical solutions and used to predict the quasi-steady speed of the drop in a wettability gradient. One solution is based on approximation of the shape of the drop as a collection of wedges, and the other is based on lubrication theory. Also, asymptotic results from both approximations for small contact angles, as well as an asymptotic result from lubrication theory that is good when the length scale of the drop is large compared with the slip length, are given. The results for the hydrodynamic force also can be used to predict the quasi-steady speed of a drop sliding down an incline.     

Enhanced mixing of droplets during coalescence on a surface with a wettability gradient

We investigated the dynamics of head-on collisions between a moving droplet and a stationary droplet on a surface with a wettability gradient. The mixing of fluids is achieved passively through convective mass transfer caused by the release of surface energy during coalescence, and also through diffusive mass transfer. The coalescence dynamics were visualized with a high-speed camera; the internal flow patterns were resolved with measurement of micro-PIV (particle image velocimetry). The results show that the released surface energy creates a pair recirculation flow inside the merged droplet when the stationary droplet is placed near the gradient, whereas most released surface energy is converted into oscillation when the stationary droplet is far from the gradient. This distinction is attributed to the motion of the contact line during coalescence. The mixing of fluorescently labeled oligonucleotides in these two modes is revealed with confocal micro-laser induced fluorescence technique. The results of 3D scans demonstrate that the motion of the contact line during coalescence distributes the fluids in a complicated manner, thus beneficial for mixing. This mechanism of enhanced mixing is applicable also for platforms other than a surface with a wettability gradient; prospective applications include improving the mixing of biochemical fluids.     

Size effect on surface tension of small droplets

We discuss the influence of the effect of droplet size on the surface tension γ and develop a self-consistent method to derive a relation between γ and the droplet radius r. Referring our expression for γ(r) to the surface of tension we recover Tolman's result.     

Flow development at the surfaces of bubbles and droplets in gradient solutions of a surfase-active liquid

The development of solutocapillary flows at the surfaces of air bubbles and chlorobenzene droplets was experimentally studied in nonuniform aqueous solutions of ethanol and isopropanol, which have a low surface tension and, hence, exhibit surface-active properties with respect to water. The experiments demonstrated the retardation of the onset of the development of the Marangoni concentration-induced convection relative to the moment of the contact between an inflowing surfactant (alcohol) and the surface. The critical concentration gradients (the Marangoni diffusion numbers) necessary for the initiation of mass transfer of a liquid along the interface were determined as dependent on the rate of inflow of a tongue of a more concentrated solution and the initial alcohol concentration around the bubble.