Cationic Hofmeister Series of Wettability Alteration in Mica-Water-Alkane Systems.

The specific interaction of ions with macromolecules and solid-liquid interfaces is of crucial importance to many processes in biochemistry, colloid science, and engineering, as first pointed out by Hofmeister in the context of (de)stabilization of protein solutions. Here, we use contact angle goniometry to demonstrate that the macroscopic contact angle of aqueous chloride salt solutions on mica immersed in ambient alkane increases from near-zero to values exceeding 10°, depending on the type and concentration of cations and pH. Our observations result in a series of increasing ability of cations to induce partial wetting in the order Na+, K+ < Li+ < Rb+ < Cs+ < Ca2+ < Mg2+ < Ba2+. Complementary atomic force microscopy measurements show that the transition to partial wetting is accompanied by cation adsorption to the mica-electrolyte interface, which leads to charge reversal in the case of divalent cations. In addition to electrostatics, hydration forces seem to play an important role, in particular for the monovalent cations.

Electroviscous Dissipation in Aqueous Electrolyte Films with Overlapping Electric Double Layers.

We use dynamic atomic force microscopy (AFM) to investigate the forces involved in squeezing out thin films of aqueous electrolyte between an AFM tip and silica substrates at variable pH and salt concentration. From amplitude and phase of the AFM signal we determine both conservative and dissipative components of the tip sample interaction forces. The measured dissipation is enhanced by up to a factor of 5 at tip-sample separations of ≈ one Debye length compared to the expectations based on classical hydrodynamic Reynolds damping with bulk viscosity. Calculating the surface charge density from the conservative forces using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary condition we find that the viscosity enhancement correlates with increasing surface charge density. We compare the observed viscosity enhancement with two competing continuum theory models: (i) electroviscous dissipation due to the electrophoretic flow driven by the streaming current that is generated upon squeezing out the counterions in the diffuse part of the electric double layer, and (ii) visco-electric enhancement of the local water viscosity caused by the strong electric fields within the electric double layer. While the visco-electric model correctly captures the qualitative trends observed in the experiments, a quantitative description of the data presumably requires more sophisticated simulations that include microscopic aspects of the distribution and mobility of ions in the Stern layer.

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl- adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl- ions will co-adsorb, thereby changing the observed ordered surface structure.

Spontaneous electrification of fluoropolymer-water interfaces probed by electrowetting.

Fluoropolymers are widely used as coatings for their robustness, water-repellence, and chemical inertness. In contact with water, they are known to assume a negative surface charge, which is commonly attributed to adsorbed hydroxyl ions. Here, we demonstrate that a small fraction of these ions permanently sticks to surfaces of Teflon AF and Cytop, two of the most common fluoropolymer materials, upon prolonged exposure to water. Electrowetting measurements carried out after aging in water are used to quantify the density of 'trapped' charge. Values up to -0.07 and -0.2 mC m-2 are found for Teflon AF and for Cytop, respectively, at elevated pH. A similar charge trapping process is also observed upon aging in various non-aqueous polar liquids and in humid air. A careful analysis highlights the complementary nature of electrowetting and streaming potential measurements in quantifying interfacial energy and charge density. We discuss the possible mechanism of charge trapping and highlight the relevance of molecular scale processes for the long term stability and performance of fluoropolymer materials for applications in electrowetting and elsewhere.

E-MALDI: optimized conditions during electrowetting-enhanced drop drying for MALDI-MS.

We recently showed that electrowetting-enhanced sample preparation for MALDI-MS (eMALDI) can increase the intensity of the MALDI signal by 2-25 times compared with conventional drop drying by concentrating all the dried sample in a single spot rather than leaving behind a heterogeneous coffee-stain pattern. Here, we demonstrate that the eMALDI signal enhancement can be further increased to more than 100 times by systematically optimizing the electrowetting actuation frequency and amplitude. This enables 30 times signal increase for a peptide standard. Simultaneously, drop drying times can be reduced approximately five times by increasing the actuation voltage and/or decreasing the initial drop volume. Copyright © 2017 John Wiley & Sons, Ltd.

Aberration control in adaptive optics: a numerical study of arbitrarily deformable liquid lenses.

By means of numerical simulations, using a computational fluid dynamics software together with an optical ray tracing analysis platform, we show that we can tune various optical aberrations by electrically manipulating the shape of liquid lenses using one hundred individually addressable electrodes. To demonstrate the flexibility of our design, we define electrode patterns based on specific Zernike modes and show that aspherical, cylindrical and decentered shapes of liquid lenses can be produced. Using different voltages, we evaluate the tuning range of spherical aberration (Z11), astigmatism (Z5 and Z6) and coma (Z7), while a hydrostatic pressure is applied to control the average curvature of a microlens with a diameter of 1mm. Upon activating all electrodes simultaneously spherical aberrations of 0.15 waves at a pressure of 30Pa can be suppressed almost completely for the highest voltages applied. For astigmatic and comatic patterns, the values of Z5, Z6 and Z7 increase monotonically with the voltage reaching values up to 0.06, 0.06 and 0.2 waves, respectively. Spot diagrams, wavefront maps and modulation transfer function are reported to quantify the optical performance of each lens. Crosstalk and independence of tunability are discussed in the context of possible applications of the approach for general wavefront shaping.

Salinity-Dependent Contact Angle Alteration in Oil/Brine/Silicate Systems: the Critical Role of Divalent Cations.

The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging. Our experiments involve aqueous droplets with a variable content of chloride salts of Na+, K+, Ca2+, and Mg2+, wetting surfaces of muscovite and amorphous silica, and an environment of ambient decane containing small amounts of fatty acids to represent polar oil components. By diluting the salt content in various manners, we demonstrate that the water contact angle on muscovite, not on silica, decreases by up to 25° as the divalent cation concentration is reduced from typical concentrations in seawater to zero. Decreasing the ionic strength at a constant divalent ion concentration, however, has a negligible effect on the contact angle. We discuss the consequences for the interpretation of core flooding experiments and the identification of a microscopic mechanism of low salinity water flooding, an increasingly popular, inexpensive, and environment-friendly technique for enhanced oil recovery.

Analytic model for the electrowetting properties of oil-water-solid systems.

The competitive wetting of oil and aqueous electrolytes on solid surfaces depends strongly on the surface charge of the solid-water and the water-oil interface. This charge density is generally not known a priori but changes as ions adsorb or desorb from or to the interfaces, depending on the composition of the fluid and the thickness of thin films of the aqueous phase that frequently arise on hydrophilic surfaces, such as minerals. We analyze the wettability of such systems by coupling standard Derjaguin-Landau-Verwey-Overbeek theory to a linearized charge regulation model. The latter is found to play an important role. By linearizing electrostatic interactions as well, we obtain a fully analytic description of transitions between different wetting scenarios as a function of the surface potentials at infinite separation and the charge regulation parameters of the two interfaces. Depending on the specific values of the regulation parameters, charge regulation is found to extend the parameter range of partial wetting and complete wetting at the expense of pseudopartial wetting and metastable wetting configurations, respectively. A specific implementation of the model is discussed for mica-water-alkane systems that was investigated in recent experiments.

Surfactant induced autophobing.

Surfactant adsorption in a three-phase system and its influence on wetting properties are relevant in various applications. Here, we report a hitherto not observed phenomenon, namely the retraction of an aqueous drop on hydrophilic solid substrates (which we refer to as 'autophobing') in ambient oil containing water-insoluble fatty acids, caused by the deposition of these fatty acids from the ambient oil onto the solid substrate. AFM measurements confirm that the surfactant is deposited on the solid by the moving contact line. This leads to a more hydrophobic substrate, the retraction of the contact line and a concomitant increase in the contact angle. The deposition process is enabled by the formation of a reaction product between deprotonated fatty acids and Ca(2+) ions at the oil/water interface. We investigate how the transition to a new equilibrium depends on the concentrations of the fatty acids, the aqueous solute, the chain lengths of the fatty acid, and the types of alkane solvent and silica or mica substrates. This phenomenon is observed on both substrates and for all explored combinations of fatty acids and solvents and thus appears to be generic. In order to capture the evolution of the contact angle, we develop a theoretical model in which the rate of adsorption at the oil-water interface governs the overall kinetics of autophobing, and transfer to the solid is determined by a mass flux balance (similar to a Langmuir Blodgett transfer).

Numerical simulation of astigmatic liquid lenses tuned by a stripe electrode.

We propose a new design for tuning the astigmatism of liquid micro-lenses using electric field and hydrostatic pressure as control parameters. We explore the feasibility and operating range of the lens with a self-consistent numerical calculation of the electric field distribution and the shape of the two-phase interface. Equilibrium shapes, including surface profiles parallel and perpendicular to a stripe electrode, are extracted to determine the astigmatism. The wavefronts are decomposed into Zernike polynomials under zero defocus conditions using a commercial ray-tracing software. We observe that the global curvature of the lens is primarily controlled by the hydrostatic pressure, while asphericity and astigmatism are controlled by the electric field. For optimized electrode geometries and simultaneous control of pressure and electric fields the astigmatism can be tuned from Z6 = 0…0.38 µm with minor changes in the focal length.

Dynamics of colloids confined in microcylinders.

We studied both global and local effects of cylindrical confinement on the diffusive behavior of hard sphere (HS) colloids. Using confocal scanning laser microscopy (CSLM) and particle tracking, we measured the mean squared displacement (MSD) of 1 micron sized silica particles in water-glycerol. This combination of fluid and setup allowed us to measure MSDs in a 4-dimensional parameter space, defined by the HS volume fraction (Φ: 0.05-0.39), cylinder radius (R: 2.5-20 micron), distance to the wall (z) and lagtime (τ: 0.03-60 s). MSDs for the entire cylinder confirm earlier findings that both narrowing the cylinder and populating it cause a slower dynamics. Additionally a decrease in R was found to cause a stronger ordering of the fluid. The effect of confinement on dynamics was further examined as a function of (z) location. For the largest cylinder (with minor curvature), we found that the strong decrease in MSD near the wall, becomes much less pronounced for higher Φ. Analyzing the radial (r) and azimuthal (θ) components, we found pronounced differences in the z-dependence that were 'hidden' in the total MSD. Near the wall, the r-MSD shows a much steeper z-dependence while at larger z, it shows a remarkable anti-correlation with the (peaked) density n(z). Also the dependence of the r-MSD on lagtime correlates with n(z): diffusive in between layers, but subdiffusive inside layers. These observations bring earlier findings together, while also shedding new light on the diffusive dynamics of concentrated colloids in narrow capillaries.

On the shape of a droplet in a wedge: new insight from electrowetting.

The equilibrium morphology of liquid drops exposed to geometric constraints can be rather complex. Even for simple geometries, analytical solutions are scarce. Here, we investigate the equilibrium shape and position of liquid drops confined in the wedge between two solid surfaces at an angle α. Using electrowetting, we control the contact angle and thereby manipulate the shape and the equilibrium position of aqueous drops in ambient oil. In the absence of contact angle hysteresis and buoyancy, we find that the equilibrium shape is given by a truncated sphere, at a position that is determined by the drop volume and the contact angle. At this position, the net normal force between drop and the surfaces vanishes. The effect of buoyancy gives rise to substantial deviations from this equilibrium configuration which we discuss here as well. We eventually show how the geometric constraint and electrowetting can be used to position droplets inside a wedge in a controlled way, without mechanical actuation.

Effects of shear and walls on the diffusion of colloids in microchannels.

Colloidal suspensions flowing through microchannels were studied for the effects of both the shear flow and the proximity of walls on the particles' self-diffusion. Use of hydrostatic pressure to pump micron-sized silica spheres dispersed in water-glycerol mixture through poly(dimethylsiloxane) channels with a cross section of 30×24µm(2), allowed variation in the local Peclet number (Pe) from 0.01 to 50. To obtain the diffusion coefficients, image-time series from a confocal scanning laser microscope were analyzed with a method that, after finding particle trajectories, subtracts the instantaneous advective displacements and subsequently measures the slopes of the mean squared displacement in the flow (x) and shear (y) directions. For dilute suspensions, the thus obtained diffusion coefficients (D(x) and D(y)) are close to the free diffusion coefficient at all shear rates. In concentrated suspensions, a clear increase with the Peclet number (for Pe > 10) is found, that is stronger for D(x) than for D(y). This effect of shear-induced collisions is counteracted by the contribution of walls, which cause a strong local reduction in D(x) and D(y).

Measuring advection and diffusion of colloids in shear flow.

An analysis of the dynamics of colloids in shear flow can be challenging because of the superposition of diffusion and advection. We present a method that separates the two motions, starting from the time-dependent particle coordinates. The restriction of the tracking to flow lanes and the subtraction of estimated advective displacements are combined in an iterative scheme that eventually makes the spatial segmentation redundant. Tracking errors due to the neglect of lateral diffusion are avoided, while drifts parallel and perpendicular to the flow are eliminated. After explaining the principles of our method, we validate it against both computer simulations and experiments. A critical overall test is provided by the mean square displacement function at high Peclet numbers (up to 50). We demonstrate via simulations how the measurement accuracy depends on diffusion coefficients and flow rates, expressed in units of camera pixels and frames. Also, sample-specific issues are addressed: inaccuracies in the velocity profile for dilute suspensions (volume fraction ≤0.03) and tracking errors for concentrated ones (VF ≥ 0.3). An analysis of experiments with colloidal spheres flowing through microchannels corroborates these findings and indicates perspectives for studies on transport, mixing, or rheology in microfluidic environments.

Stick-Slip to Sliding Transition of Dynamic Contact Lines under AC Electrowetting.

We show that at low velocities the dynamics of a contact line of a water drop moving over a Teflon-like surface under ac electrowetting must be described as stick-slip motion, rather than one continuous movement. At high velocities we observe a transition to a slipping regime. In the slipping regime the observed dependence of the contact angle is well described by a linearization of both the hydrodynamic and the molecular-kinetic model for the dynamic contact line behavior. The overall geometry of the drop also has a strong influence on the contact angle: if the drop is confined to a disk-like shape with radius R, much larger than the capillary length, and height h, smaller than the capillary length, the advancing angle increases steeper with velocity as the aspect ratio h/R is smaller. Although influence of the flow field near a contact line on the contact angle behavior has also been observed in other experiments, these observations do not fit either model. Finally, in our ac experiments no sudden increase of the hysteresis beyond a certain voltage and velocity was observed, as reported by other authors for a dc voltage, but instead we find with increasing voltage a steady decrease of the hysteresis.

High speed adaptive liquid microlens array.

Liquid microlenses are attractive for adaptive optics because they offer the potential for both high speed actuation and parallelization into large arrays. Yet, in conventional designs, resonances of the liquid and the complexity of driving mechanisms and/or the device architecture have hampered a successful integration of both aspects. Here we present an array of up to 100 microlenses with synchronous modulation of the focal length at frequencies beyond 1 kHz using electrowetting. Our novel concept combines pinned contact lines at the edge of each microlens with an electrowetting controlled regulation of the pressure that actuates all microlenses in parallel. This design enables the development of various shapes of microlenses. The design presented here has potential applications in rapid parallel optical switches, artificial compound eye and three dimensional imaging.

Electrowetting driven optical switch and tunable aperture.

We demonstrate an electrowetting based optical switch with tunable aperture. Under the influence of an electric field a non-transparent oil film can be replaced locally by a transparent water drop creating an aperture through which light can pass. Its diameter can be tuned between 0.2 and 1.2 mm by varying the driving voltage or frequency. The on and off response time of the switch is in the order of 2 and 120 ms respectively. Finally we demonstrate an array of switchable apertures that can be tuned independently or simultaneously.

Colloidal dynamics near a particle-covered surface.

How the diffusive dynamics of colloidal spheres changes in the vicinity of a particle-coated surface is of importance for industrial challenges such as fouling and sedimentation as well as for fundamental studies into confinement effects. We addressed this question by studying colloidal dynamics in a partially coated surface layer, using video microscopy. Particle mean squared displacement (MSD) functions were measured as a function of a (local) effective volume fraction (EVF), which was varied by making use of gravity settling. Comparison of MSDs at the bare and coated surfaces for EVF of 0.2-0.4 revealed that at the latter surface the motion amplitudes are strongly reduced, accompanied by a sharp transition from diffusive to nearly caged motion. This clearly indicates that the surface-attached particles cannot be taken into account via volume fraction and that their immobility has a distinct effect. For EVF > 0.45, the caging becomes dominated by the suspended particles, making the dynamics at the bare and coated surfaces similar.

Electrical switching of wetting states on superhydrophobic surfaces: a route towards reversible Cassie-to-Wenzel transitions.

We demonstrate that the equilibrium shape of the composite interface between superhydrophobic surfaces and drops in the superhydrophobic Cassie state under electrowetting is determined by the balance of the Maxwell stress and the Laplace pressure. Energy barriers due to pinning of contact lines at the edges of the hydrophobic pillars control the transition from the Cassie to the Wenzel state. Barriers due to the narrow gap between adjacent pillars control the lateral propagation of the Wenzel state. We demonstrate how reversible switching between the two wetting states can be achieved locally using suitable surface and electrode geometries.

Anisotropic and hindered diffusion of colloidal particles in a closed cylinder.

Video microscopy and particle tracking were used to measure the spatial dependence of the diffusion coefficient (D(α)) of colloidal particles in a closed cylindrical cavity. Both the height and radius of the cylinder were equal to 9.0 particle diameters. The number of trapped particles was varied between 1 and 16, which produced similar results. In the center of the cavity, D(α) turned out to be 0.75D(0) measured in bulk liquid. On approaching the cylindrical wall, a transition region of about 3 particle diameters wide was found in which the radial and azimuthal components of D(α) decrease to respective values of 0.1D(0) and 0.4D(0), indicating asymmetrical diffusion. Hydrodynamic simulations of local drag coefficients for hard spheres produced very good agreement with experimental results. These findings indicate that the hydrodynamic particle-wall interactions are dominant and that the complete 3D geometry of the confinement needs to be taken into account to predict the spatial dependence of diffusion accurately.