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Revisiting derivations of Gibbs adsorption equation show its applicability to solid surfaces without limiting requirement of constant state of strain. Some attempts to use such a restriction to prove the correctness of the Shuttleworth equation have failed. Also, we have shown that the mandatory conditions for the Maxwell's relations make its inapplicable for the description of capillary and electrocapillary phenomena on solid surfaces, as they lead, if used correctly, to trivial results - known Gibbs adsorbtion equation and Lippmann electrocapillary equation. Attempts to use Maxwell's relations for the case of solid electrodes available in the literature are based on mathematical defects and, consequently, yield erroneous results.

Lateral-flow immunosensing devices continue to be the most successful commercial realization of analytical microdevices. They owe their success to their simplicity, which significantly depends on the capillary-driven flow and versatile technological platform that lends itself to fast and low-cost product development. To compete with such a convenient product, microsystems can benefit from simple-to-operate fluid manipulation. We show that the capillary-driven flow in microchannels can be manipulated with electrochemically activated valves with no moving parts. These valves consist of screen-printed electrode pairs that are transversal to the flow. One of the electrodes is solvent-etched to produce a superhydrophobic surface that provides passive stopping and facilitates low-voltage (~1 V) actuation of the flow via electrowetting. The operation of such valves in the stop-go mode, with a response time between 2 and 45 sec depending on the type and concentration of salt, is demonstrated. Mechanistic investigations indicated that the response depends on at least three phenomena that contribute to electrocapillarity: the electrochemical double-layer capacitance, specific counterion adsorption, and possible electrohydrodynamic effects.

Unknown phenomenon was observed on the oxidized surface of a number of metals in water solutions including nickel, palladium, and platinum. Elastic extension of the metal decreases the interface capacity in wide potential region which reaches 0.4 V in the case of palladium. Within such region, the oscillograms “estance vs. potential” disclose an unusually long and low flat section which may be considered as the expanded zero of the differential charge density. The decrease of the capacity points out strengthening the bond of the water molecules to the surface oxide under its elastic extension which thickens the hydrated envelops of the adsorbed ions. Along the flat section, the state of the interface is reversible without changing the structure of the surface oxide. The anodic boundary of the flat section can be used as a sign of reaching the oxide monolayer. In the equations of solid state electrocapillarity, the potential of zero charge is presented explicitly. Its derivative with respect to elastic deformation is independent of the electrode potential and shifts the reversible section of the estance curve along the ordinate.

This work focuses on performing the homogenization of the Nernst-Planck-Poisson system, in order to obtain an efficient modelling of the ionic transfer and electrocapillary effects at the macroscopic scale for saturated porous media. The homogenization is performed with the powerful two-scale convergence method, which enables to obtain both the homogenized model and the associated convergence result.

Impregnating the pores of nanoporous gold with aqueous electrolyte yields a hybrid nanomaterial with two separate and interpenetrating charge transport paths, electronic conduction in the metal and ionic conduction in the electrolyte. As the two paths are capacitively connected, space-charge layers along the internal interfaces are coupled to electric potential differences between the paths and can be controlled or detected thereby. The present experiments show that the space charge couples to mechanical deformation of the hybrid material, so that external loading generates an electric current. The electric signal originates from charge displacement along the entire internal interface; the signal is particularly robust since the interface area is large. The charge transfer in response to load constitutes a piezoelectric response, yet the mechanism is quite different to classic piezoelectricity. The analysis in this work predicts links between electromechanical coupling parameters for strain sensing and actuation, which are in excellent agreement with the experiment.

We analyze the effect of asymmetric finite ion size in nanoconfinement in the view of osmotic pressure and electrocapillarity. When the confinement width becomes comparable with the Debye length, the overlapped electric double layer is significantly deformed by the steric effects. We derive the osmotic pressure from the modified Poisson-Boltzmann equation in a nanoslit to examine the deviation from the ideal osmotic pressure and the repulsive force on the wall considering the asymmetry of ion sizes. Then the electrocapillarity due to the steric effect is investigated under constant potential condition with the flat interface assumption. Later, the deformation by the electrocapillarity is also considered in the first order approximation.

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension. Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries. Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude ( 500 mN/m to near zero). Furthermore, this method requires only a very modest potential (< 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests.

The adhesion between colloidal silica particles and modified electrodes has been studied by direct force measurements with the colloidal probe technique based on the atomic force microscope (AFM). The combination of potentiostatic control of gold electrodes and chemical modification of their surface with self-assembled monolayers (SAMs) allows for the decoupling of forces due to the electrical double layers and functional groups at the solid/liquid interface. Adhesion on such electrodes can be tuned over a large range using the externally applied potential and the aqueous solution's ionic strength. By utilizing cantilevers with a high force constant, it is possible to separate the various contributions to adhesion in an unambiguous manner. These contributions comprise diffuse-layer overlap, van der Waals forces, solvent exclusion, and electrocapillarity. A quantitative description of the observed adhesion forces is obtained by taking into account the surface roughness of the silica particle. The main component of the adhesion forces originates from the overlap of the electrical double layers, which is tuned by the external potential. By contrast, effects due to electrocapillarity are of only minor importance. Based on our quantitative analysis, a new approach is proposed that allows tuning of the adhesion force as a function of the externally applied potential. We expect this approach to have important applications for the design of microelectromechanical systems (MEMS), the development of electrochemical sensors, and the application of micro- and nanomanipulation.

Contrary to some recent publications, the trivial definition of the surface charge density q = Q/A does not give any information about the charge Q and area A. Therefore this definition cannot be used as a “simple check,” rejecting results of electrochemical experiments where the values Q and A are the independent variables. Experimental confirmation and practical applications can be the two self-contained checks for the equations of solid-state electrocapillarity. Along with thermodynamics, the kinetic aspect is important here since the charge and area can oscillate in the large frequency range. Cycling the surface charge gives the three different contributions to the alternating surface tension of solids, corresponding to the double layer charging, reversible chemisorption, and discrete transitions closed within the rigid surface layer. The derivative of the charge density with respect to elastic deformation represents chemisorption and can be decreased to negligibly small value at the point of zero charge by increasing the frequency. On the base of the solid-state electrocapillarity, the dependence between the adsorption energy and elastic deformation was measured for the first time. It was thus found that stretching reinforces the bonding of hydrogen to the platinum surface. Acting inside the rigid surface monolayer, the alternating surface tension of solids is an independent tool in solving some complex problems of electrochemistry and solid-state physics. Two consecutive transitions are discovered on platinum instead of two coexistent hydrogen states which earlier were associated with two waves of the charging current. There are three consecutive hydrogen states separated along the potential axis by transitions from one state to another. Similar surface transitions are observed also on iridium, rhodium, and palladium. The number of transitions coincides with the number of finite radial nodes of the wave functions formed by d-electrons of these metals.

Electrocapillarity is the basis of modern electrowetting. And room temperature ionic liquids, an increasingly important set of electrolytes and organic salts that are liquid at room temperature, are considered a novel class of electrowetting agents, because of non-significant vapor pressure, nonflammability, good thermal stability, and a wide useable temperature range. In this paper, a simple device has been fabricated to investigate the electrocapillarity of ionic liquids. It shows attractive features involving wide operating temperature and in particular high stability, fast response and good reversibility at high temperatures. Besides, electrocapillarity of ionic liquids is strongly dependent on power supply frequency. In particular, high frequency, stable, reversible and wide height of rise modulations were obtained. The phenomenon of ionic liquids-based electrocapillarity was found to be affected by the structure and physicochemical properties of ionic liquids such as density, surface tensio...

Capacitance distribution of {(Ni(0.6)Nb(0.4)(1-x)Zrx}(100-y)-Hy (x = 0.30, 0.35, 0.40, 0.45 and 0.50, 0 < or = y < or = 20) glassy alloy ribbons was carried out by ac impedance analysis at frequency of 1 kHz, in terms of a distributed constant equivalent circuit. The capacitance can be represented by oblique contour lines. The highest capacitance (1-11 microF) could be found near the point when x = 0.40, y = 10, which is a composition occurring room-temperature Coulomb oscillation, while capacitance of the composition (x = 0.35, y = 4) occurring ballistic transport was around 0.8 microF. The capacitance difference would be explained by an effect of hydrogen localization derived from morphology of distorted Zr-centered icosahedral Zr5Ni5Nb3 clusters and ideal Ni-centered clusters. The electrocapillarity equation showed that the specific capacitance between two electrodes increases parabolic with decreasing the distance, as a polarized glutinous liquid.

Experiments on solid-phase electrosurface migration through formally inert eutectic WO3|MeWO4 interfaces in symmetric electrochemical cells such as Pt|WO3|MeWO4|WO3|Pt are performed. It is shown that the most significant changes occur at the “cathode” interface (−)Pt|WO3|MeWO4|, where counter electrosurface drawing of WO3 to the inner surface of MeWO4 ceramics (with the formation of two-phase distributed composite WO3|MeWO4) and a much smaller flow of Me2+ components to the WO3 ceramics depth are observed. Scanning and transmission electron microscopy showed the formation of nano- and microscale objects of various shape in grain boundaries’ regions, among which well-faceted nanoobjects shaped as ribbons and rods from a few to hundreds of nanometers thick are noticeable. The Ca and Sr contents in WO3(−) cathode pellets after experiments in cells are determined by X-ray fluorescence analysis, scanning electron microscopy, energy-dispersive analysis, and depth profiling using glow-discharge spectrometry. The data obtained are interpreted based on the concepts of solid-phase electrocapillarity (WO3 migration) and electrochemical intercalation of Me into the WO3 structure.

Electrowetting is an electrocapillary phenomenon, i.e. the surface charge generated at the solid-liquid interface through an external voltage improves the wettability in the system. The Young-Lippmann equation provides the simplest thermodynamic framework and describes electrowetting adequately. Saturation, i.e. the reduced or nullified effectiveness of the external voltage below a threshold contact angle value, was and remains the most controversial issue in the physics of electrowetting. A simple estimation of the limits of validity of the Young model is obtained by setting the solid-liquid interfacial tension to zero. This approach predicts acceptably the change in electrowetting mechanism but not the minimal value of the contact angle achievable during electrowetting. The mechanism of saturation is, in all probability, related to charge injection into the dielectric layer insulating the working electrode but physical details are scarce. Surface force and spectroscopic techniques should be deployed in order to improve our understanding of the surface charging of insulators immersed in conductive liquids. Electrowetting in solid-liquid-liquid systems is generally more effective and robust. Electrowetting offers new ways of studying the dynamics of liquid movement as it allows selective changes in the wettability of the system. Refereed/Peer-reviewed

This review describes the evolution of important concepts related to potential drops at interfaces in electrochemical systems. The role of the thermodynamic theory of electrocapillarity of perfectly polarizable electrodes in the development of interfacial electrochemistry is emphasized. A critical analysis of the phenomenological models of the electrical double layer on ideally polarizable electrodes is given. Certain trends in studying solid electrodes with well-defined surfaces brought into contact with electrolyte solutions are summarized. Attention is drawn to several unsolved problems crucial for the future development of electrochemical surface science. Finally, some recent experimental data are analyzed for selected models.

This paper presents analytical and experimental study of electrocapillarity in dielectrics under the frame work of parallel plates using palm oil.. First, Mathematical approach was used to derive an expression relating capillary ascent with the applied field. The results obtained from the experiment and that of the analytical results were compared with the expected results from the equation relating the liquid ascent and the applied field obtained from Lippmann equation, where it was observed that there is no evidence of linear relation between the height of the capillary rise of oil in the tube and the applied field.

In this article, a multiphysics approach is used to develop a model for microdroplet motion and dynamics in contemporary electrocapillary-based digital microfluidic systems. Electrostatic and hydrodynamic pressure effects are combined to calculate the driving and opposing forces as well as the moving boundary of the microdroplet. The proposed methodology accurately predicts the microdroplet electrohydrodynamics which is crucial for the design, control and fabrication of such devices. The results obtained from the model are in excellent agreement with expected trends and experimental results.

The ultraslow relaxation, on the order of a few seconds or longer, of the structure of the electrical double layer in response to the change in the phase-boundary potential across the ionic liquid (IL)|water(W) interface, which was recently reported for trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, has been confirmed in two new hydrophobic ionic liquids, trihexyltetradecylphosphonium bis(nonafluorobutanesulfonyl)amide and trihexyltetradecylphosphonium tetrakis(pentafluorophenyl)borate. A comparison of the degree of the hysteresis in electrocapillary curves for these ILs with those for trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide demonstrates that the degree of the hysteresis is not correlated with the viscosity of these ILs. The ultraslow relaxation of the electrical double layer seems to be a general feature of ILs at electrified interfaces. Keywords: Liquid|liquid interface, Ionic liquid|water interface, Electrical double layer, Ionic liquid, Relaxation, Ultraslow relaxation, Electrocapillarity, Electrocapillary curves, Trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, Tetradecyltrihexylphosphonium bis(nonafluorobutanesulfonyl)amide, Tetradecyltrihexylphosphonium tetrakis(pentafluorophenyl)borate

We use a three-dimensional multiphase lattice-Boltzmann model to study basic operations such as transport, merging and splitting of nanoliter water droplets actuated by electrowetting in digital microfluidic devices. In a first step, numerical and analytical predictions for the droplet transport velocity are compared and very good agreement is obtained for a wide range of contact angles. The same algorithm is employed then to study the dynamics of the splitting processes at different contact angles and different geometries of the cell. The configuration of the liquid droplet involved in a splitting process and the dependence of the splitting time on the transport velocity are also investigated and phenomenological laws describing these processes are also proposed.

A new model has been formulated for the electrochemical instability at the liquid∣liquid interface, for which only a rudimentary model [T. Kakiuchi, J. Electroanal. Chem. 536 (2002) 63–69] had been available. The new model considers the diffuse double layers in the presence of the specifically adsorbed surface-active ions, whose adsorption Gibbs energy linearly varies with the phase-boundary potential. The electrocapillary equation in the presence of the common ions partitioning in both phases is employed under the assumption that the partition of the surface-active ions is described by the Nernst equation. The excess surface charge due to the specific adsorption of surface-active ions is allowed for in calculating the structure of the diffuse part of the electrical double layers on both sides of the interface. The calculated electrocapillary curves agree with the experimental results. It is confirmed that electrocapillary curves can have positive curvature in a certain potential region, which signifies the presence of an instability window.

Electrocapillarity has been studied in detail at the interface between a hydrophobic ionic liquid (IL), trioctylmethylammonium bis(nonafluorobutanesulfonyl)amide, and water, where the ultraslow relaxation of the structure of the electrical double layer on the IL side of the interface exists. The response of the interfacial tension and that of the charging current to the potential step can be fitted by a double exponential model having the relaxation time constants of a few seconds and 100 s. The hysteresis in the interfacial tension in the IL diluted with nitrobenzene persists even in an almost 1:1 mixture of the IL and nitrobenzene. The thermodynamically definable double layer capacitance (C(dl)) estimated from the equilibrated electrocapillary curve, that is, the interfacial tension versus potential curve, at the IL|water interface has a maximum value of about 60 microF cm(-2) in the vicinity of the potential of zero charge (pzc) when the aqueous phase is 0.1 mol dm(-3) LiCl. The C(dl) versus the potential plot shows a characteristic camelback shape, showing a shallow minimum at the pzc, where the C(dl) value is 42 microF cm(-2). This minimum seems to reflect the contribution of C(dl) on the aqueous side of the interface to the total capacitance.

In response to the rapid advances in microelectronics, novel cooling technologies are needed to meet increasing cooling requirements. As a paradigm-shifting technique, electrowetting-on-dielectric (EWOD) uses electric potential to control the movement of a liquid droplet on a dielectric surface. In this work, we developed an EWOD-based microfluidic technique for active and adaptive thermal management of on-chip hot spots. A two-dimensional array of control electrodes was patterned on the chip surface for EWOD operations. By applying DC or AC voltages with appropriate sequence and timing to the electrode units, we were able to transport microdroplets of tens of μL along a programmable path. Without the need of external pumps and valves, the droplets were precisely delivered to cooling targets. With the driving voltage as low as 40 VAC, we demonstrate high heat flux (7.6 W/cm2) cooling on a hot spot. The EWOD-induced internal circulation within the droplets led to a time-averaged Nusselt number of ~45.

The fundamental building blocks of typical electrowetting-on-dielectric (EWOD) actuation and their importance in the EWOD mechanism are introduced and reviewed, respectively. The emphasis in this experimental study of EWOD is on dielectric materials, upon which the performance of EWOD devices is heavily dependent. Dielectric breakdown of several typical polymeric and inorganic insulators employed as dielectrics for EWOD has been analytically investigated, which is forced to occur between the electrodes and conductive liquids under certain threshold potential. The electric breakdown occurring in both dielectric layer and surrounding medium (air or silicon oil) has been studied to build up a mathematical model of breakdown voltage as a function of dielectric thickness. Contact angle measurement of some polymeric materials and self-assembled monolayer using pure water has been carried out to demonstrate the contact angle tunability and reversibility, respectively, upon EWOD actuation.

This paper reports the design, fabrication, and testing of a liquid-metal (LM) droplet-based radio-frequency microelectromechanical systems (RF MEMS) shunt switch with dc-40 GHz performance. The switch demonstrates better than 0.3 dB insertion loss and 20 dB isolation up to 40 GHz, achieving significant improvements over previous LM-based RF MEMS switches. The improvement is attributed to use of electrowetting on dielectric (EWOD) as a new actuation mechanism, which allows design optimized for RF switching. A two-droplet design is devised to solve the biasing problem of the actuation electrode that would otherwise limit the performance of a single-droplet design. The switch design uses a microframe structure to accurately position the liquid-solid contact line while also absorbing variations in deposited LM volumes. By sliding the liquid-solid contact line electrostatically through EWOD, the switch demonstrates bounceless switching, low switch-on time (60 mus), and low power consumption (10 nJ per cycle).

Liquid-metal (LM) droplet-based MEMS switches have mostly been restricted to slow applications until now due to the following reasons: (1) a relatively large switching gap (distance) needed to accommodate imprecise volumes and locations of droplets on the device and (2) lack of high-speed actuation to move the droplets quickly across the switching gap. To combat these problems, we explore switching by sliding the solid-LM-gas triple contact line rather than the entire droplet. This new approach allows us to use a microframe, which not only consistently positions the LM droplet but also makes the switching gap less sensitive to the errors in the deposited-droplet volume, allowing us to design microswitches with very small switching gaps (e.g., 10 mum for 600 mum-diameter droplets). Furthermore, a study of electrowetting-on-dielectric identifies a regime of fast contact-line sliding at the onset of droplet spreading. By moving the contact line fast across a small switching distance, we demonstrate a low-latency LM switch with 60 mus switch-on latency ( ~ 20 times better than other LM-switch technologies) and better than 5 mus signal rise/fall time, while boasting no contact bounce, as expected from an LM switch. High power-handling capability and long-term reliability are also discussed.

The design, fabrication, and optical properties of tunable liquid microoptical components based on electrowetting are presented. Two optical microsystems are discussed: a single liquid microlens with tunable focal length, centered and stabilized in a micromachined positioning structure, and laterally repositionable tunable liquid microlens arrays. The latter employs electrowetting for lateral movement as well as focal length tuning of the optical elements. Through the use of novel microstructuring techniques, a high positioning accuracy may be achieved with low electrode count.

This paper presents a robust anodic Ta2O5 dielectric as an alternative insulator for fabricating low-voltage electrowetting on dielectric (EWOD) systems. Previously reported low-voltage EWOD technologies require high-temperature processes ( > 435degC), which unlike this room temperature technology, are not compatible with standard copper and aluminum integrated circuit interconnect technology as well as polymer-based substrates. The anodized Ta2O5 forms a uniform pinhole free layer with a surface roughness (R a) of 0.6 nm. This robust film enables an ultrathin amorphous FluoroPolymer layer to be employed to reduce the EWOD driving voltage to 13 V. Both sub-20-nm Teflon-AF and CYTOP layers have been successfully coated on top of Ta2O5 with good adhesion. Applying voltages of 6-15 V significantly modified the contact angles of droplets in air on these samples (121deg to 81deg on Teflon-AF at 13 V and 114deg to 95deg on CYTOP at 6 V). Successful 14-V EWOD manipulation involving droplets being dispensed from a reservoir, their movement, followed by merging them together has been demonstrated using devices using a Teflon-AF + Ta2O5 dielectric.

A hydrodynamic scaling model of droplet actuation in an electrowetting-on-dielectric (EWD) actuator is presented that takes into account the effects of contact angle hysteresis, drag from the filler fluid, drag from the solid walls, and change in the actuation force while a droplet traverses a neighboring electrode. Based on this model, the threshold voltage, VT, for droplet actuation is estimated as a function of the filler medium of a scaled device. It is shown that scaling models of droplet splitting and liquid dispensing all show a similar scaling dependence on [t/er(d/L)]1/2, where t is insulator thickness and d/L is the aspect ratio of the device. It is also determined that reliable operation of a EWD actuator is possible as long as the device is operated within the limits of the Lippmann–Young equation. The upper limit on applied voltage, Vsat, corresponds to contact-angle saturation. The minimum 3-electrode splitting voltages as a function of aspect ratio d/L < 1 for an oil medium are less than Vsat. However, for an air medium the minimum voltage for 3-electrode droplet splitting exceeds Vsat for d/L ≥ 0.4. EWD actuators were fabricated to operate with droplets down to 35pl. Reasonable scaling results were achieved.

We demonstrate effective mixing of microliter droplets using electrically tunable superhydrophobic nanostructured surfaces. By applying electrical voltage and current, droplets can be reversibly switched from a wetting to a non-wetting state, which induces fluid motion within the droplet. This mixing concept was verified using a DNA hybridization assay, in which a single droplet reversibility accelerated the hybridization reaction by an order of magnitude as compared to mixing by passive diffusion. This work offers a new method to effectively mix droplets for a variety of microfluidics applications.

We have demonstrated a 2D droplet manipulation platform allowing fully optical manipulation of droplets on a photosensitive surface. Optically controlled injection, transport, separation, and multiple droplet manipulation have been achieved for nanoliter-size droplets. These functions are realized by sandwiching the droplets between two optoelectrowetting (OEW) surfaces. Optical illumination on OEW surfaces changes the surface wettability locally through the electrowetting mechanism. Optical illumination turns the initially Teflon-coated surface from hydrophobic to hydrophilic. This process is reversible and can be controlled in real time. We have achieved a maximum transport speed of 78 mm/s for a 100-nL droplet using a scanning laser beam. We have also demonstrated a fully decoupled 2D multidroplet manipulation on the OEW surfaces. Potentially, the OEW mechanism can be scaled up to process a large number of liquid droplets using projected optical images for high throughput applications.

This paper describes highly efficient in-droplet particle concentration and separation where particles are concentrated and separated into droplets by traveling-wave dielectrophoresis (DEP) and subsequent electrowetting-on-dielectric droplet splitting. A successful concentration for 5-mum aldehyde sulfate (AS) latex particles was experimentally achieved using microfabricated devices, showing that 98% of the total particles were concentrated into a split daughter droplet. In addition, in-droplet particle separation was successfully achieved using the following two different cases of particle mixtures: case 1) a mixture of 5-mum AS latex beads and 8-mum glass beads; and case 2) a mixture of ground pine (GP) spores and 8-mum glass beads. In case 1), 97% of the total AS beads were separated into one split droplet and 77% of the total glass beads into the other split droplet. In case 2), over 92% of the GP spores were separated into a split daughter droplet, whereas 86% of the glass beads were separated into the other split daughter droplet. In all these concentration and separation experiments, the applied frequency and the conductivity medium are key parameters influencing the concentration and separation performance, which have been optimally determined by measuring the DEP and electrorotation spectra of the used particles prior to the concentration and separation experiments. This integrated in-droplet separation and concentration method may provide an additional functionality to digital microfluidics.

Large changes in stress (of order GPa) are observed with relatively modest variations in applied potential (on the order of 500 mV), even in nonspecifically adsorbing electrolyte solutions. Here we...

An innovative and simple microfabrication method for digital microfluidics is presented. In this method, devices are formed from copper substrates or gold compact disks using rapid marker masking to replace photolithography. The new method is capable of forming devices with inter-electrode gaps as small as 50 μm. Saran™ wrap (polyethylene film) and commercial water repellants were used as dielectric and hydrophobic coatings, respectively, to replace commonly used and more expensive materials such as parylene-C and Teflon-AF. Devices formed by the new method enabled single- and two-plate actuation of droplets with volumes of 1–12 μL. Fabricated devices were successfully tested for droplet manipulation, merging and splitting. We anticipate that this fabrication method will bring digital microfluidics within the reach of any laboratory with minimal facilities.

The electrochemical polarisation of metal catalyst films on solid electrolyte substrates can basically lead to three different effects: (a) the generation of mobile surface species (spillover) which spread over the catalyst surface and modify the catalytic activity, (b) potential-controlled segregation of impurities in the catalyst and (c) potential-dependent surface energy (electrocapillarity). The generation of spillover species occurs at the three-phase boundary between metal, solid electrolyte and gas phase and is highly localized. The spreading occurs via diffusion and leads to time-dependent and inhomogeneous surface concentrations. The kinetics of the spillover process can only be observed with in situ surface-analytical techniques in combination with electrochemical methods which offer sufficient resolution in space and time. Model experiments with UV and X-ray photoelectron emission microscopy (PEEM and SPEM) are summarized and discussed with respect to their relevance for the better understanding of electrochemical promotion in catalysis.

We observe aperiodic mechanical oscillations of a drop of oxidant solution placed around an iron stick on a mercury surface. These oscillations are explained as a visual manifestation of electrochemical oscillations at the iron–solution interface that, via electrocapillarity, lead to changes of the surface tension at the drop's bottom.

Unsteady filling of electrolyte solution inside a nanochannel by the electrocapillarity effect is studied. The filling rate is predicted as a function of the bulk concentration of the electrolyte, the surface potential (or surface charge density), and the cross sectional shape of the channel. For a nanochannel, the average outward normal stress exerted on the cross section of a channel $({\overline{P}}_{zz}^{})$ can be regarded as a measure of electrocapillarity and it is the driving force of the flow. This electrocapillarity measure is first analyzed by using the solution of the Poisson-Boltzmann equation. From the analysis, it is found that the results for many different cross sectional shapes can be unified with good accuracy if the hydraulic radius is adopted as the characteristic length scale of the problem. Especially in the case of constant surface potential, for both limits of $\ensuremath{\kappa}h\ensuremath{\rightarrow}0$ and $\ensuremath{\kappa}h\ensuremath{\rightarrow}\ensuremath{\infty}$, it can be shown theoretically that the electrocapillarity is independent of the cross sectional shape if the hydraulic radius is the same. In order to analyze the geometric effects more systematically, we consider the regular $N$-polygons with the same hydraulic radius and the rectangles of different aspect ratios. Washburn's approach is then adopted to predict the filling rate of electrolyte solution inside a nanochannel. It is found that the average filling velocity decreases as $N$ increases in the case of regular $N$-polygons with the same hydraulic radius. This is because the regular $N$-polygons of the same hydraulic radius share the same inscribing circle.

International audience; Formation mechanism of emulsification is being studied by using “electrocapillarity” which had been once developed to study the structure of "electrical-double layer”. First the characteristics of electrocapillary curve of KCl aqueous solution/Hg system used for the cold model have been investigated to understand the ionic structure near the interface in comparison with the case of real (liquid CaO-SiO2-Al2O3/liquid steel) system. Then the emulsification phenomena at the meniscus (the interface) with and without imposing the electric potential have been observed by using a high speed camera. Finally the mechanisms of newly found phenomena have been discussed by taking account of the theory of electrocaoillarity.

Liquid metals based on gallium, such as eutectic gallium indium (EGaIn) and Galinstan, have been integrated as static components in microfluidic systems for a wide range of applications including soft electrodes, pumps, and stretchable electronics. However, there is also a possibility to continuously pump liquid metal into microchannels to create shape reconfigurable metallic structures. Enabling this concept necessitates a simple method to control dynamically the path the metal takes through branched microchannels with multiple outlets. This paper demonstrates a novel method for controlling the directional flow of EGaIn liquid metal in complex microfluidic networks by simply applying a low voltage to the metal. According to the polarity of the voltage applied between the inlet and an outlet, two distinct mechanisms can occur. The voltage can lower the interfacial tension of the metal via electrocapillarity to facilitate the flow of the metal towards outlets containing counter electrodes. Alternatively, the voltage can drive surface oxidation of the metal to form a mechanical impediment that redirects the movement of the metal towards alternative pathways. Thus, the method can be employed like a 'valve' to direct the pathway chosen by the metal without mechanical moving parts. The paper elucidates the operating mechanisms of this valving system and demonstrates proof-of-concept control over the flow of liquid metal towards single or multiple directions simultaneously. This method provides a simple route to direct the flow of liquid metal for applications in microfluidics, optics, electronics, and microelectromechanical systems.

Carbon nanotube sponges are lightweight, conductive, highly porous, and flexible. An integration of these properties is suitable for constructing high-performance electrocapillary imbibers. Water imbibition into the sponges can be initiated at low potentials with tunable uptake rates and switched on and off reversibly. These controllable nanoporous imbibers have potential applications in a wide range of flexible micro- and nanofluidic systems.

Non-Newtonian fluids can present a complex rheological behaviour involving shear-thinning, viscoelastic or thixotropic effects. We focus here on the characterization of generalized Newtonian fluids as shear-thinning fluids. Rotational rheometers are torque-sensitive, which makes the measurement of viscosity at low shear-rates very difficult, in particular for low viscosity fluids. An accurate knowledge of this value is, however, particularly important for the characterization of several types of flows, in particular those featuring a free surface, a symmetry axis or a symmetry plane. The experimental determination of viscosity and surface tension is enabled from the propagation of attenuated capillary waves. An optical technique has been implemented in order to determine the shear-thinning viscosity at values of the shear-rate as small as 10-3s-1 from measurements of the spatial attenuation and wavelength. We have performed measurements on two different polymer solutions, we show that this technique is complementary to the classical rotational rheometer techniques since it gives access to the zero shear viscosity, which could not be measured by using rotational rheometers. The present technique is thus used to characterize the Newtonian plateau, while a rotational rheometer is used to characterize the fluid behaviour at moderate to high shear rates. � 2014 Elsevier B.V.

This paper studies and characterizes electrowetting-on-dielectric (EWOD) actuations on coplanar electrodes with an electrode-free cover plate or no cover plate. By arranging driving and reference electrodes on one plate, such an EWOD configuration can accommodate more sensing mechanisms from above and thus allows increased flexibility for system development. Various coplanar electrodes are tested for contact angle changes by EWOD with a focus on the effect of the percentage gap between electrodes and are found to be in good agreement with a simple analytical model. The droplet-moving devices demonstrate the successful moving, cutting and merging of droplets (~0.1 µl) in a parallel-plate configuration, i.e., between the driving plate with coplanar electrodes and the passive plate with no electrode. EWOD actuation in single plate configuration, i.e. no cover plate, is also demonstrated, adding additional flexibility for the system design.

Electrowetting (EW) induced droplet motion has been explored in the past decade in view of its promising applications in the field of microfluidics. This paper demonstrates the potential of energy-based analyses for modeling the performance of EW-based fluid actuation systems. Analyses based on system energy minimization offer simplified modeling tools to predict the overall performance of EW systems while circumventing the need to model the numerous complexities in the system. An analytical model is developed to estimate the actuation force on a droplet moving between two electrodes. The origins and contributions of various components of the actuation force are analyzed. The effects of dielectric parameters, electrode layout, droplet geometry and shape are discussed with the objective of maximizing the actuation force. The actuation force model is combined with semi-analytical models for predicting the forces opposing droplet motion to develop a model that predicts transient EW-induced droplet motion. Parametric results are obtained to evaluate the importance of operating voltage, fluid properties and droplet geometry on droplet motion.

The electrocapillary curve and temporal stability of the interfacial tension were measured for a polarized flat water–dichloroethane interface under electrochemical instability. The interfacial tension was measured on the basis of capillary wave spectra obtained by means of the heterodyne detection of the light scattered at the interface. Anomalous behavior of the electrocapillary curve was observed in the potential range in which the electrochemical instability was expected. The correlation between the interfacial tension and the current spike observed in the chronoamperometry was examined. Despite the presence of the anomalous current spikes and other phenomena showing thermodynamic instability, the results revealed that the interfacial tension was stable and did not show any correlation with the anomalous current. The results were explained by a structure formation by the lateral mass transfer to avoid the instability, in addition to the vertical interfacial ion transfer which is apparently observed by the current measurement.