Controlling the distance of highly confined droplets in a capillary by interfacial tension for merging on-demand.

Droplet microfluidics is a powerful technology that finds many applications in chemistry and biomedicine. Among different configurations, droplets confined in a capillary (or plugs) present a number of advantages: they allow positional identification and simplify the integration of complex multi-steps protocols. However, these protocols rely on the control of droplet speed, which is affected by a complex and still debated interplay of various physico-chemical parameters like droplet length, viscosity ratio between droplets and carrier fluid, flow rate and interfacial tension. We present here a systematic investigation of the droplet speed as a function of their length and interfacial tension, and propose a novel, simple and robust methodology to control the relative distance between consecutive droplets flowing in microfluidic channels through the addition of surfactants either into the dispersed and/or into the continuous phases. As a proof of concept application, we present the possibility to accurately trigger in space and time the merging of two confined droplets flowing in a uniform cross-section circular capillary. This approach is further validated by monitoring a conventional enzymatic reaction used to quantify the concentration of H2O2 in a biological sample, showing its potentialities in both continuous and stopped assay methods.

Dynamics of Ferrofluid Drops on Magnetically Patterned Surfaces.

The motion of liquid drops on solid surfaces is attracting a lot of attention because of its fundamental implications and wide technological applications. In this article, we present a comprehensive experimental study of the interaction between gravity-driven ferrofluid drops on very slippery oil-impregnated surfaces and a patterned magnetic field. The drop speed can be accurately tuned by the magnetic interaction, and more interestingly, drops are found to undergo a stick-slip motion whose contrast and phase can be easily tuned by changing either the strength of the magnetic field or the ferrofluid concentration. This motion is the result of the periodic modulation of the external magnetic field and can be accurately analyzed because the intrinsic pinning due to chemical defects is negligible on oil-impregnated surfaces.

Highly sticky surfaces made by electrospun polymer nanofibers.

We report on a comprehensive study of the unique adhesive properties of mats of polymethylmethacrylate (PMMA) nanofibers produced by electrospinning. Fibers are deposited on glass, with varying of the diameter and the relative orientation of the polymer filaments (random vs. aligned configuration). While no significant variation is observed in the static contact angle (∼130°) of deposited water drops upon changing the average fiber diameter up to the micrometer scale, fibers are found to exhibit unequalled water adhesion. Placed vertically, they can hold up water drops as large as 60 µL, more than twice the values typically obtained with hairy surfaces prepared by different methods. For aligned fibers with anisotropic wetting behavior, the maximum volume measured in the direction perpendicular to the fibers goes up to 90 µL. This work suggests new routes to tailor the wetting behavior on extended areas by nanofiber coatings, with possible applications in adsorbing and catalytic surfaces, microfluidic devices, and filtration technologies.

Sliding drops across alternating hydrophobic and hydrophilic stripes.

We perform a joint numerical and experimental study to systematically characterize the motion of 30 µl drops of pure water and of ethanol in water solutions, sliding over a periodic array of alternating hydrophobic and hydrophilic stripes with a large wettability contrast and a typical width of hundreds of microns. The fraction of the hydrophobic areas has been varied from about 20% to 80%. The effects of the heterogeneous patterning can be described by a renormalized value of the critical Bond number, i.e., the critical dimensionless force needed to depin the drop before it starts to move. Close to the critical Bond number we observe a jerky motion characterized by an evident stick-slip dynamics. As a result, dissipation is strongly localized in time, and the mean velocity of the drops can easily decrease by an order of magnitude compared to the sliding on the homogeneous surface. Lattice Boltzmann numerical simulations are crucial for disclosing to what extent the sliding dynamics can be deduced from the computed balance of capillary, viscous, and body forces by varying the Bond number, the surface composition, and the liquid viscosity. Beyond the critical Bond number, we characterize both experimentally and numerically the dissipation inside the droplet by studying the relation between the average velocity and the applied volume forces.

Tuning drop motion by chemical patterning of surfaces.

We report the results of extensive experimental studies of the sliding of water drops on chemically heterogeneous surfaces formed by square and triangular hydrophobic domains printed on glass surfaces and arranged in various symmetric patterns. Overall, the critical Bond number, that is, the critical dimensionless force needed to depin the drop, is found to be strongly affected by the shape and the spatial arrangement of the domains. Soon after the droplet begins to move, stick-slip motion is observed on all surfaces, although it is less pronounced than that on striped surfaces. On the triangular patterns, anisotropic behavior is found with drops sliding down faster when the tips of the glass hydrophilic triangles are pointing in the down-plane direction. Away from the critical Bond number, the dynamic regime depends mainly on the static contact angle and weakly on the actual surface pattern. Lattice Boltzmann numerical simulations are performed to validate the experimental results and test the importance of the viscous ratio between the droplet phase and the outer phase.

Stick-slip sliding of water drops on chemically heterogeneous surfaces.

We present a comprehensive study of water drops sliding down chemically heterogeneous surfaces formed by a periodic pattern of alternating hydrophobic and hydrophilic stripes. Drops are found to undergo a stick-slip motion whose average speed is an order of magnitude smaller than that measured on a homogeneous surface having the same static contact angle. This motion is the result of the periodic deformations of the drop interface when crossing the stripes. Numerical simulations confirm this view and are used to elucidate the principles underlying the experimental observations.

Suspension of water droplets on individual pillars.

We report results of extensive experimental and numerical studies on the suspension of water drops deposited on cylindrical pillars having circular and square cross sections and different wettabilities. In the case of circular pillars, the drop contact line is pinned to the whole edge contour until the drop collapses due to the action of gravity. In contrast, on square pillars, the drops are suspended on the four corners and spilling along the vertical walls is observed. We have also studied the ability of the two geometries to sustain drops and found that if we compare pillars with the same characteristic size, the square is more efficient in pinning large volumes, while if we normalize the volumes to pillar areas, the opposite is true.

Nanofriction of neon films on superconducting lead.

With a quartz crystal microbalance technique we have studied the nanofriction of neon monolayers deposited on a lead surface at a temperature around 7 K. Unlike heavier adsorbates, Ne is found to systematically slide at such low temperatures without any evidence of pinning. The crossing of the Pb superconducting-metal transition is not accompanied by any change in dissipation, suggesting that the electronic contribution to friction is negligible for this system.

Probing the equilibrium dynamics of colloidal hard spheres above the mode-coupling glass transition.

We use dynamic light scattering and computer simulations to study equilibrium dynamics and dynamic heterogeneity in concentrated suspensions of colloidal hard spheres. Our study covers an unprecedented density range and spans seven decades in structural relaxation time, tau(alpha0, including equilibrium measurements above phi(c), the location of the glass transition deduced from fitting our data to mode-coupling theory. Instead of falling out of equilibrium, the system remains ergodic above phi(c) and enters a new dynamical regime where tau(alpha) increases with a functional form that was not anticipated by previous experiments, while the amplitude of dynamic heterogeneity grows slower than a power law with tau(alpha), as found in molecular glass formers close to the glass transition.

Direct experimental evidence of a growing length scale accompanying the glass transition.

Understanding glass formation is a challenge, because the existence of a true glass state, distinct from liquid and solid, remains elusive: Glasses are liquids that have become too viscous to flow. An old idea, as yet unproven experimentally, is that the dynamics becomes sluggish as the glass transition approaches, because increasingly larger regions of the material have to move simultaneously to allow flow. We introduce new multipoint dynamical susceptibilities to estimate quantitatively the size of these regions and provide direct experimental evidence that the glass formation of molecular liquids and colloidal suspensions is accompanied by growing dynamic correlation length scales.