Evaporation and Electrowetting of Sessile Droplets on Slippery Liquid-Like Surfaces and Slippery Liquid-Infused Porous Surfaces (SLIPS).

Sessile droplet evaporation underpins a wide range of applications from inkjet printing to coating. However, drying times can be variable and contact-line pinning often leads to undesirable effects, such as ring stain formation. Here, we show voltage programmable control of contact angles during evaporation on two pinning-free surfaces. We use an electrowetting-on-dielectric approach and Slippery Liquid-Infused Porous (SLIP) and Slippery Omniphobic Covalently Attached Liquid-Like (SOCAL) surfaces to achieve a constant contact angle mode of evaporation. We report evaporation sequences and droplet lifetimes across a broad range of contact angles from 105°-67°. The values of the contact angles during evaporation are consistent with expectations from electrowetting and the Young-Lippman equation. The droplet contact areas reduce linearly in time, and this provides estimates of diffusion coefficients close to the expected literature value. We further find that the total time of evaporation over the broad contact angle range studied is only weakly dependent on the value of the contact angle. We conclude that on these types of slippery surfaces, droplet lifetimes can be predicted and controlled by the droplet's volume and physical properties (density, diffusion coefficient, and vapor concentration difference to the vapor phase) largely independent of the precise value of contact angle. These results are relevant to applications, such as printing, spraying, coating, and other processes, where controlling droplet evaporation and drying is important.

Liquid marbles: topical context within soft matter and recent progress.

The study of particle stabilized interfaces has a long history in terms of emulsions, foams and related dry powders. The same underlying interfacial energy principles also allow hydrophobic particles to encapsulate individual droplets into a stable form as individual macroscopic objects, which have recently been called "Liquid Marbles". Here we discuss conceptual similarities to superhydrophobic surfaces, capillary origami, slippery liquids-infused porous surfaces (SLIPS) and Leidenfrost droplets. We provide a review of recent progress on liquid marbles, since our earlier Emerging Area article (Soft Matter, 2011, 7, 5473-5481), and speculate on possible future directions from new liquid-infused liquid marbles to microarray applications. We highlight a range of properties of liquid marbles and describe applications including detecting changes in physical properties (e.g. pH, UV, NIR, temperature), use for gas sensing, synthesis of compounds/composites, blood typing and cell culture.

Dielectrowetting driven spreading of droplets.

The wetting of solid surfaces can be modified by altering the surface free energy balance between the solid, liquid, and vapor phases. Here we show that liquid dielectrophoresis induced by nonuniform electric fields can be used to enhance and control the wetting of dielectric liquids. In the limit of thick droplets, we show theoretically that the cosine of the contact angle follows a simple voltage squared relationship analogous to that found for electrowetting on dielectric. Experimental observations confirm this predicted dielectrowetting behavior and show that the induced wetting is reversible. Our findings provide a noncontact electrical actuation process for meniscus and droplet control.

Evaluation of a microfluidic device for the electrochemical determination of halide content in ionic liquids.

A microfluidic device designed for electrochemical studies on a microliter scale has been utilized for the examination of impurity levels in ionic liquids (ILs). Halide impurities are common following IL synthesis, and this study demonstrates the ability to quantify low concentrations of halide in a range of ILs to levels of approximately 5 ppm, even in ILs not currently measurable using other methods such as ion chromatography. To validate the mixer device, the electrochemistry of ferrocene was also examined and compared with spectroscopic and bulk electrochemistry measurements. An automated "sample preparation, delivery, and calibration" method was developed, and the chip successfully used for linear sweep, cyclic voltammetry (under both quiescent and steady-state flowing conditions), square wave voltammetry, and differential pulse voltammetry. An effective method of electrochemically cleaning the electrodes is also presented.

Learning from superhydrophobic plants: the use of hydrophilic areas on superhydrophobic surfaces for droplet control.

In many countries, the mornings in spring are graced with spectacular displays of dew drops hanging on spiders' webs and on leaves. Some leaves, in particular, sport particularly large droplets that last well into the morning. In this paper, we study a group of plants that show this effect on their superhydrophobic leaves to try to discover how and why they do it. We describe the structures they use to gather droplets and suggest that these droplets are used as a damper to absorb kinetic energy allowing water to be redirected from sideways motion into vertical motion. Model surfaces in the shape of leaves and as more general flat sheets show that this principle can be used to manipulate water passively, such as on the covers of solar panels, and could also be used in parts of microfluidic devices. The mode of transport can be switched between rolling droplets and rivulets to maximize control.

Nano-scale superhydrophobicity: suppression of protein adsorption and promotion of flow-induced detachment.

Wall adsorption is a common problem in microfluidic devices, particularly when proteins are used. Here we show how superhydrophobic surfaces can be used to reduce protein adsorption and to promote desorption. Hydrophobic surfaces, both smooth and having high surface roughness of varying length scales (to generate superhydrophobicity), were incubated in protein solution. The samples were then exposed to flow shear in a device designed to simulate a microfluidic environment. Results show that a similar amount of protein adsorbed onto smooth and nanometer-scale rough surfaces, although a greater amount was found to adsorb onto superhydrophobic surfaces with micrometer scale roughness. Exposure to flow shear removed a considerably larger proportion of adsorbed protein from the superhydrophobic surfaces than from the smooth ones, with almost all of the protein being removed from some nanoscale surfaces. This type of surface may therefore be useful in environments, such as microfluidics, where protein sticking is a problem and fluid flow is present. Possible mechanisms that explain the behaviour are discussed, including decreased contact between protein and surface and greater shear stress due to interfacial slip between the superhydrophobic surface and the liquid.

Bimorph material/structure designs for high sensitivity flexible surface acoustic wave temperature sensors.

A fundamental challenge for surface acoustic wave (SAW) temperature sensors is the detection of small temperature changes on non-planar, often curved, surfaces. In this work, we present a new design methodology for SAW devices based on flexible substrate and bimorph material/structures, which can maximize the temperature coefficient of frequency (TCF). We performed finite element analysis simulations and obtained theoretical TCF values for SAW sensors made of ZnO thin films (~5 µm thick) coated aluminum (Al) foil and Al plate substrates with thicknesses varied from 1 to 1600 µm. Based on the simulation results, SAW devices with selected Al foil or plate thicknesses were fabricated. The experimentally measured TCF values were in excellent agreements with the simulation results. A normalized wavelength parameter (e.g., the ratio between wavelength and sample thickness, λ/h) was applied to successfully describe changes in the TCF values, and the TCF readings of the ZnO/Al SAW devices showed dramatic increases when the normalized wavelength λ/h was larger than 1. Using this design approach, we obtained the highest reported TCF value of -760 ppm/K for a SAW device made of ZnO thin film coated on Al foils (50 µm thick), thereby enabling low cost temperature sensor applications to be realized on flexible substrates.

Voltage-induced spreading and superspreading of liquids.

The ability to quickly spread a liquid across a surface and form a film is fundamental for a diverse range of technological processes, including printing, painting and spraying. Here we show that liquid dielectrophoresis or electrowetting can produce wetting on normally non-wetting surfaces, without needing modification of the surface topography or chemistry. Additionally, superspreading can be achieved without needing surfactants in the liquid. Here we use a modified Hoffman-de Gennes law to predict three distinct spreading regimes: exponential approach to an equilibrium shape, spreading to complete wetting obeying a Tanner's law-type relationship and superspreading towards a complete wetting film. We demonstrate quantitative experimental agreement with these predictions using dielectrophoresis-induced spreading of stripes of 1,2 propylene glycol. Our findings show how the rate of spreading of a partial wetting system can be controlled using uniform and non-uniform electric fields and how to induce more rapid superspreading using voltage control.

Faraday rotation data analysis with least-squares elliptical fitting.

A method of analyzing Faraday rotation data from pulsed magnetic field measurements is described. The method uses direct least-squares elliptical fitting to measured data. The least-squares fit conic parameters are used to rotate, translate, and rescale the measured data. Interpretation of the transformed data provides improved accuracy and time-resolution characteristics compared with many existing methods of analyzing Faraday rotation data. The method is especially useful when linear birefringence is present at the input or output of the sensing medium, or when the relative angle of the polarizers used in analysis is not aligned with precision; under these circumstances the method is shown to return the analytically correct input signal. The method may be pertinent to other applications where analysis of Lissajous figures is required, such as the velocity interferometer system for any reflector (VISAR) diagnostics. The entire algorithm is fully automated and requires no user interaction. An example of algorithm execution is shown, using data from a fiber-based Faraday rotation sensor on a capacitive discharge experiment.

Small volume laboratory on a chip measurements incorporating the quartz crystal microbalance to measure the viscosity-density product of room temperature ionic liquids.

A microfluidic glass chip system incorporating a quartz crystal microbalance (QCM) to measure the square root of the viscosity-density product of room temperature ionic liquids (RTILs) is presented. The QCM covers a central recess on a glass chip, with a seal formed by tightly clamping from above outside the sensing region. The change in resonant frequency of the QCM allows for the determination of the square root viscosity-density product of RTILs to a limit of approximately 10 kg m(-2) s(-0.5). This method has reduced the sample size needed for characterization from 1.5 ml to only 30 mul and allows the measurement to be made in an enclosed system.

All solids, including teflon, are hydrophilic (to some extent), but some have roughness induced hydrophobic tendencies.

It has recently been argued on the basis of four experiments that Teflon can often be regarded as hydrophilic when considering the interaction between liquid water and the solid surface of Teflon [Gao and McCarthy, Langmuir 2008, 24, 9183-9188]. The authors also recommend that more recognition be given to "hydrophilic" and "hydrophobic" as qualitative adjectives and discuss the importance of advancing and receding contact angles. In this work, I use net surface free energy changes for events consisting of (i) a smooth solid wrapping a droplet of water and (ii) a grain attaching to a droplet, to show that all solids with a Young's law contact angle thetae<180 degrees can be considered absolutely hydrophilic. This terminology is true in the sense that attachment of the solid to the liquid is always preferred even though the relative strength decreases as theta(e) increases. However, I also demonstrate that, within a surface free energy model, solids with thetae>90 degrees can be regarded as possessing hydrophobic tendencies with increasing roughness. The effect of the bending rigidity of the substrate is discussed, and a condition for minimum droplet radius for wrapping to occur is given.

Levitation-free vibrated droplets: resonant oscillations of liquid marbles.

A spherical conducting droplet in an alternating electric field is known to undergo shape oscillations. When the droplet is supported by a substrate, the shape is no longer a complete sphere, but shape resonances are still observed. To obtain a completely spherical droplet, some kind of levitation is needed, unless the droplet is in microgravity, and this has previously been provided by gas films or magnetic or other external forces. In this work, we report observations of shape oscillations of a hydrophobic-powder-coated droplet of water. A droplet of water rolled on a hydrophobic powder self-coats such that the water becomes encapsulated as a liquid marble. When the powder is a spherical hydrophobic grain with a contact angle greater than 90 degrees , it adheres to the solid-water interface with more than half of its diameter projecting from the liquid, thus ensuring the encapsulated water does not come into contact with any substrate. These liquid marbles are highly mobile and can be regarded as completely nonwetting droplets possessing contact angles of 180 degrees . In this work, we show that they also provide a new mechanism equivalent to levitating droplets and provide droplets with small contact areas and completely mobile contact lines for studies of shape oscillations. Liquid marbles were created using hydrophobic lycopodium and droplets of water containing potassium chloride and were excited into motion using an electrowetting-on-dielectric configuration with applied frequency swept from 1 to 250 Hz. Both an up-and-down motion and an oscillation involving multiple nodes were observed and recorded using a high-speed camera. The resonant oscillation modes of small liquid marbles were fitted to the theory for vibrations of a free spherical volume of fluid. This work demonstrates the principle that oscillation modes of completely nonwetting droplets can be studied using a simple powder coating approach without the need for an active mechanism for levitation.

Cassie and Wenzel: were they really so wrong?

The properties of superhydrophobic surfaces are often understood by reference to the Cassie-Baxter and Wenzel equations. Recently, in a paper deliberately entitled to be provocative, it has been suggested that these equations are wrong; a suggestion said to be justified using experimental data. In this paper, we review the theoretical basis of the equations. We argue that these models are not so much wrong as have assumptions that define the limitations on their applicability and that with suitable generalization they can be used with surfaces possessing some types of spatially varying defect distributions. We discuss the relationship of the models to the previously published experiments and using minimum energy considerations review the derivations of the equations for surfaces with defect distributions. We argue that this means the roughness parameter and surface area fractions are quantities local to the droplet perimeter and that the published data can be interpreted within the models. We derive versions of the Cassie-Baxter and Wenzel equations involving roughness and Cassie-Baxter solid fraction functions local to the three-phase contact line on the assumption that the droplet retains an average axisymmetry shape. Moreover, we indicate that, for superhydrophobic surfaces, the definition of droplet perimeter does not necessarily coincide with the three-phase contact line. As a consequence, the three-phase contact lines within the contact perimeter beneath the droplet can be important in determining the observed contact angle on superhydrophobic surfaces.

Decoupling of the liquid response of a superhydrophobic quartz crystal microbalance.

Recent reports using particle image velocimetry and cone-and-plate rheometers have suggested that a simple Newtonian liquid flowing across a superhydrophobic surface demonstrates a finite slip length. Slippage on a superhydrophobic surface indicates that the combination of topography and hydrophobicity may have consequences for the coupling at the solid--liquid interface observed using the high-frequency shear-mode oscillation of a quartz crystal microbalance (QCM). In this work, we report on the response of a 5 MHz QCM possessing a superhydrophobic surface to immersion in water--glycerol mixtures. QCM surfaces were prepared with a layer of SU-8 photoresist and lithographically patterned to produce square arrays of 5 mum diameter circular cross-section posts spaced 10 microm center-to-center and with heights of 5, 10, 15, and 18 microm. Non-patterned layers were also created for comparison, and both non-hydrophobized and chemically hydrophobized surfaces were investigated. Contact angle measurements confirmed that the hydrophobized post surfaces were superhydrophobic. QCM measurements in water before and after applying pressure to force a Cassie-Baxter (non-penetrating) to Wenzel (penetrating) conversion of state showed a larger frequency decrease and higher dissipation in the Wenzel state. QCM resonance spectra were fitted to a Butterworth-van Dyke model for the full range of water-glycerol mixtures from pure water to (nominally) pure glycerol, thus providing data on both energy storage and dissipation. The data obtained for the post surfaces show a variety of types of behavior, indicating the importance of the surface chemistry in determining the response of the quartz crystal resonance, particularly on topographically structured surfaces; data for hydrophobized post surfaces imply a decoupling of the surface oscillation from the mixtures. In the case of the 15 microm tall hydrophobized post surfaces, crystal resonance spectra become narrower as the viscosity-density product increases, which is contrary to the usual behavior. In the most extreme case of the 18 microm tall hydrophobized post surfaces, both the frequency decrease and bandwidth increase of the resonance spectra are significantly lower than that predicted by the Kanazawa and Gordon model, thus implying a decoupling of the oscillating surface from the liquid, which can be interpreted as interfacial slip.

Electrowetting of nonwetting liquids and liquid marbles.

Transport of a water droplet on a solid surface can be achieved by differentially modifying the contact angles at either side of the droplet using capacitive charging of the solid-liquid interface (i.e., electrowetting-on-dielectric) to create a driving force. Improved droplet mobility can be achieved by modifying the surface topography to enhance the effects of a hydrophobic surface chemistry and so achieve an almost complete roll-up into a superhydrophobic droplet where the contact angle is greater than 150 degrees . When electrowetting is attempted on such a surface, an electrocapillary pressure arises which causes water penetration into the surface features and an irreversible conversion to a state in which the droplet loses its mobility. Irreversibility occurs because the surface tension of the liquid does not allow the liquid to retract from these fixed surface features on removal of the actuating voltage. In this work, we show that this irreversibility can be overcome by attaching the solid surface features to the liquid surface to create a liquid marble. The solid topographic surface features then become a conformable "skin" on the water droplet both enabling it to become highly mobile and providing a reversible liquid marble-on-solid system for electrowetting. In our system, hydrophobic silica particles and hydrophobic grains of lycopodium are used as the skin. In the region corresponding to the solid-marble contact area, the liquid marble can be viewed as a liquid droplet resting on the attached solid grains (or particles) in a manner similar to a superhydrophobic droplet resting upon posts fixed on a solid substrate. When a marble is placed on a flat solid surface and electrowetting performed it spreads but with the water remaining effectively suspended on the grains as it would if the system were a droplet of water on a surface consisting of solid posts. When the electrowetting voltage is removed, the surface tension of the water droplet causes it to ball up from the surface but carrying with it the conformable skin. A theoretical basis for this electrowetting of a liquid marble is developed using a surface free energy approach.

Layer guided-acoustic plate mode biosensors for monitoring MHC-peptide interactions.

The transduction signals from the immobilisation of a class I heavy chain, HLA-A2, on a layer guided acoustic plate mode device, followed by binding of beta(2)-microglobulin and subsequent selective binding of a target peptide are reported.

Wetting and wetting transitions on copper-based super-hydrophobic surfaces.

Rough and patterned copper surfaces were produced using etching and, separately, using electrodeposition. In both of these approaches the roughness can be varied in a controlled manner and, when hydrophobized, these surfaces show contact angles that increase with increasing roughness to above 160 degrees . We show transitions from a Wenzel mode, whereby the liquid follows the contours of the copper surface, to a Cassie-Baxter mode, whereby the liquid bridges between features on the surface. Measured contact angles on etched samples could be modeled quantitatively to within a few degrees by the Wenzel and Cassie-Baxter equations. The contact angle hysteresis on these surfaces initially increased and then decreased as the contact angle increased. The maximum occurred at a surface area where the equilibrium contact angle would suggest that a substantial proportion of the surface area was bridged.

Analysis of droplet evaporation on a superhydrophobic surface.

The evaporation process for small, 1-2-mm-diameter droplets of water from patterned polymer surfaces is followed and characterized. The surfaces consist of circular pillars (5-15 microm diameter) of SU-8 photoresist arranged in square lattice patterns such that the center-to-center separation between pillars is 20-30 microm. These types of surface provide superhydrophobic systems with theoretical initial Cassie-Baxter contact angles for water droplets of up to 140-167 degrees, which are significantly larger than can be achieved by smooth hydrophobic surfaces. Experiments show that on these SU-8 textured surfaces water droplets initially evaporate in a pinned contact line mode, before the contact line recedes in a stepwise fashion jumping from pillar to pillar. Provided the droplets of water are deposited without too much pressure from the needle, the initial state appears to correspond to a Cassie-Baxter one with the droplet sitting upon the tops of the pillars. In some cases, but not all, a collapse of the droplet into the pillar structure occurs abruptly. For these collapsed droplets, further evaporation occurs with a completely pinned contact area consistent with a Wenzel-type state. It is shown that a simple quantitative analysis based on the diffusion of water vapor into the surrounding atmosphere can be performed, and estimates of the product of the diffusion coefficient and the concentration difference (saturation minus ambient) are obtained.

A general approach to selection of multiple cubic volume elements using the ISIS technique.

The ISIS method is used regularly for the selection of a single cubic volume of tissue for in vivo investigation by high-resolution NMR spectroscopy. This technique has been extended on a theoretical basis to include the simultaneous selection of a number of cubes, the signals from which can be either assessed individually or in certain circumstances coadded to produce improvement in signal-to-noise ratio. The modification requires additional selective RF pulses in the spatial encoding prepulse period, and spatially localized spectra are produced by addition and subtraction of NMR signals in a manner similar to the original ISIS technique.