Wetting phenomena are ubiquitous in nature and technology. A solid substrate exposed to the environment is almost invariably covered by a layer of fluid material. In this review, the surface forces that lead to wetting are considered, and the equilibrium surface coverage of a substrate in contact with a drop of liquid. Depending on the nature of the surface forces involved, different scenarios for wetting phase transitions are possible; recent progress allows us to relate the critical exponents directly to the nature of the surface forces which lead to the different wetting scenarios. Thermal fluctuation effects, which can be greatly enhanced for wetting of geometrically or chemically structured substrates, and are much stronger in colloidal suspensions, modify the adsorption singularities. Macroscopic descriptions and microscopic theories have been developed to understand and predict wetting behavior relevant to microfluidics and nanofluidics applications. Then the dynamics of wetting is examined. A drop, placed on a substrate which it wets, spreads out to form a film. Conversely, a nonwetted substrate previously covered by a film dewets upon an appropriate change of system parameters. The hydrodynamics of both wetting and dewetting is influenced by the presence of the three-phase contact line separating "wet" regions from those that are either dry or covered by a microscopic film only. Recent theoretical, experimental, and numerical progress in the description of moving contact line dynamics are reviewed, and its relation to the thermodynamics of wetting is explored. In addition, recent progress on rough surfaces is surveyed. The anchoring of contact lines and contact angle hysteresis are explored resulting from surface inhomogeneities. Further, new ways to mold wetting characteristics according to technological constraints are discussed, for example, the use of patterned surfaces, surfactants, or complex fluids.

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Wetting and Spreading

Electrowetting has become one of the most widely used tools for manipulating tiny amounts of liquids on surfaces. Applications range from 'lab-on-a-chip' devices to adjustable lenses and new kinds of electronic displays. In the present article, we review the recent progress in this rapidly growing field including both fundamental and applied aspects. We compare the various approaches used to derive the basic electrowetting equation, which has been shown to be very reliable as long as the applied voltage is not too high. We discuss in detail the origin of the electrostatic forces that induce both contact angle reduction and the motion of entire droplets. We examine the limitations of the electrowetting equation and present a variety of recent extensions to the theory that account for distortions of the liquid surface due to local electric fields, for the finite penetration depth of electric fields into the liquid, as well as for finite conductivity effects in the presence of AC voltage. The most prominent failure of the electrowetting equation, namely the saturation of the contact angle at high voltage, is discussed in a separate section. Recent work in this direction indicates that a variety of distinct physical effects?rather than a unique one?are responsible for the saturation phenomenon, depending on experimental details. In the presence of suitable electrode patterns or topographic structures on the substrate surface, variations of the contact angle can give rise not only to continuous changes of the droplet shape, but also to discontinuous morphological transitions between distinct liquid morphologies. The dynamics of electrowetting are discussed briefly. Finally, we give an overview of recent work aimed at commercial applications, in particular in the fields of adjustable lenses, display technology, fibre optics, and biotechnology-related microfluidic devices.

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Electrowetting: from basics to applications

Intermolecular And Surface Forces

Fundamental and applied research in chemistry and biology benefits from opportunities provided by droplet-based microfluidic systems. These systems enable the miniaturization of reactions by compartmentalizing reactions in droplets of femoliter to microliter volumes. Compartmentalization in droplets provides rapid mixing of reagents, control of the timing of reactions on timescales from milliseconds to months, control of interfacial properties, and the ability to synthesize and transport solid reagents and products. Droplet-based microfluidics can help to enhance and accelerate chemical and biochemical screening, protein crystallization, enzymatic kinetics, and assays. Moreover, the control provided by droplets in microfluidic devices can lead to new scientific methods and insights.

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Reactions in Droplets in Microfluidic Channels

We describe devices in which optics and fluidics are used synergistically to synthesize novel functionalities. Fluidic replacement or modification leads to reconfigurable optical systems, whereas the implementation of optics through the microfluidic toolkit gives highly compact and integrated devices. We categorize optofluidics according to three broad categories of interactions: fluid–solid interfaces, purely fluidic interfaces and colloidal suspensions. We describe examples of optofluidic devices in each category.

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Developing optofluidic technology through the fusion of microfluidics and optics

The rapid developments in biotechnology create a great demand for fluid handling systems on the nano- and picoliter scale. The characterization of minute quantities of DNA or protein samples requires highly integrated, automated, and miniaturized total analysis systems (-TAS). The small scales necessitate new concepts for devices both from a technological and from a fundamental physical point of view. Here, we describe recent trends in both areas. New technologies include soft lithography, chemical, and topographical structuring of surfaces in order to define pathways for liquids, as well as electrowetting for manipulation purposes. Fundamentally, the interplay between geometric confinement and the size of biological macromolecules gives rise to complex dynamic behavior. The combination of both fluorescence imaging and scattering techniques allows for detailed insight into the dynamics of individual molecules and into their self-assembly into supramolecular aggregates.

Trends in Microfluidics with Complex Fluids

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 i...

https://pubs.acs.org/doi/pdf/10.1021/acs.langmuir.6b04470

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

Electrowetting is a versatile tool to reduce the apparent contact angle of partially wetting conductive liquids by several tens of degrees via an externally applied voltage. We studied various fundamental and applied aspects of equilibrium liquid surface morphologies both theoretically and experimentally. Our theoretical analysis showed that surface profiles on homogeneous surfaces display a diverging curvature in the vicinity of the three phase contact line. The asymptotic contact angle at the contact line is equal to Young's angle, independent of the applied voltage. With respect to the morphology of the liquid surface, contact angle variations achieved by electrowetting are equivalent to those achieved by varying the chemical nature of the substrates, except for electric field-induced distortions in a region close to the contact line. Experimentally, we studied the (global) morphology of liquid microstructure substrates with stripe-shaped electrodes. As the local contact angle is reduced by increasing the applied voltage, liquid droplets elongate along the stripe axis as expected. For droplets on a single surface with a stripe electrode, there is a discontinuous morphological transition where elongated droplets transform into translationally invariant cylinder segments with the contact line pinned along the stripe edge and vice versa. If the liquid is confined between two parallel surfaces with parallel stripe electrodes, the elongation of the droplet and its transformation into a translationally invariant morphology with pinned contact lines is continuous. Experimental results are compared to analytical and numerical models.

https://iopscience.iop.org/article/10.1088/0953-8984/17/9/016/pdf

Electrowetting: a convenient way to switchable wettability patterns

We investigate the spreading at variable rate of a water drop on a smooth hydrophobic substrate in an ambient oil bath driven by electrowetting. We find that a thin film of oil is entrapped under the drop. Its thickness is described by an extension of the Landau-Levich law of dip coating that includes the electrostatic pressure contribution. Once trapped, the thin film becomes unstable under the competing effects of the electrostatic pressure and surface tension and dewets into microscopic droplets, in agreement with a linear stability analysis. Our results recommend electrowetting as an efficient experimental approach to the fundamental problem of dynamic wetting in the presence of a tunable substrate-liquid interaction.

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Friedrich Gunther Mugele

Papers

Trends in Microfluidics with Complex Fluids

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

Electrowetting: a convenient way to switchable wettability patterns

Electrowetting-induced oil film entrapment and instability.

Electrowetting-induced oil film entrapment and instability