Morphology and stability of droplets sliding on soft viscoelastic substrates.

We show that energy dissipation partition between a liquid and a solid controls the shape and stability of droplets sliding on viscoelastic gels. When both phases dissipate energy equally, droplet dynamics is similar to that on rigid solids. When the solid is the major contributor to dissipation, we observe an apparent contact angle hysteresis of viscoelastic origin. We find excellent agreement between our data and a non-linear model of the wetting of gels of our own that also indicates the presence of significant slip. Our work opens general questions on the dynamics of curved contact lines on compliant substrates.

Dramatic Slowing Down of Oil/Water/Silica Contact Line Dynamics Driven by Cationic Surfactant Adsorption on the Solid.

We report on the contact line dynamics of a triple-phase system silica/oil/water. When oil advances onto silica within a water film squeezed between oil and silica, a rim forms in water and recedes at constant velocity. We evidence a sharp (three orders of magnitude) decrease of the contact line velocity upon the addition of cationic surfactants above a threshold concentration, which is slightly smaller than the critical micellar concentration. We show that, with or without surfactant, and within the range of small capillary numbers investigated, the contact line dynamics can be described by a friction term that does not reduce to pure hydrodynamical effects. In addition, we derive a model that successfully accounts for the selected contact line velocity of the rim. We further demonstrate the strong increase of the friction coefficient with surfactant bulk concentration results from the strongly nonlinear adsorption isotherm of surfactants on silica. From the variations of the friction coefficient and spreading parameter with surface concentration, we suggest a picture in which the part of the adsorbed surfactants that are strongly bound to the silica interface is trapped under the oil droplet and is responsible for the large increase in line friction.

Nonlinear theory of wetting on deformable substrates.

The spreading of a liquid over a solid material is a key process in a wide range of applications. While this phenomenon is well understood when the solid is undeformable, its "soft" counterpart is still misunderstood and no consensus has been reached with regard to the physical mechanisms ruling the spreading of liquid drops over soft deformable materials. In this work we provide a theoretical framework, based on the nonlinear theory of discontinuities, to describe the behavior of a triple line on a soft material. We show that the contact line motion is opposed both by nonlinear localized capillary and visco-elastic forces. We give an explicit analytic formula relating the dynamic contact angle of a moving drop to its velocity for arbitrary rheology. We then specialize this formula to the experimentally relevant case of elastomers with the Chasset-Thirion (power-law) type of rheologies. The theoretical prediction is in very good agreement with experimental data, without any adjustable parameters. We then show that the nonlinear force balance presented in this work can also be used to recover classical models of wetting. Finally we provide predictions for the dynamic behavior of the yet largely unexplored case of a viscous drop spreading over a soft visco-elastic material and predict the emergence of a new form of apparent hysteresis.

Elastocapillary Ridge as a Noninteger Disclination.

Understanding the interfacial properties of solids with their environment is a crucial problem in fundamental science and applications. Elastomers have challenged the scientific community in this respect, and a satisfying description is still missing. Here, we argue that the interfacial properties of elastomers, such as their wettability, can be understood with a nonlinear elastic model with the assumption of a strain-independent surface energy. We show that our model captures accurately available data on elastomer wettability and discuss its implications.

Geometrical control of dissipation during the spreading of liquids on soft solids.

Gel layers bound to a rigid substrate are used in cell culture to control differentiation and migration and to lower the friction and tailor the wetting of solids. Their thickness, often considered a negligible parameter, affects cell mechanosensing or the shape of sessile droplets. Here, we show that the adjustment of coating thickness provides control over energy dissipation during the spreading of flowing matter on a gel layer. We combine experiments and theory to provide an analytical description of both the statics and the dynamics of the contact line between the gel, the liquid, and the surrounding atmosphere. We extract from this analysis a hitherto-unknown scaling law that predicts the dynamic contact angle between the three phases as a function of the properties of the coating and the velocity of the contact line. Finally, we show that droplets moving on vertical substrates coated with gel layers having linear thickness gradients drift toward regions of higher energy dissipation. Thus, thickness control opens the opportunity to design a priori the path followed by large droplets moving on gel-coated substrates. Our study shows that thickness is another parameter, besides surface energy and substrate mechanics, to tune the dynamics of liquid spreading and wetting on a compliant coating, with potential applications in dew collection and free-surface flow control.

Growth and relaxation of a ridge on a soft poroelastic substrate.

Elastocapillarity describes the deformations of soft materials by surface tensions and is involved in a broad range of applications, from microelectromechanical devices to cell patterning on soft surfaces. Although the vast majority of elastocapillarity experiments are performed on soft gels, because of their tunable mechanical properties, the theoretical interpretation of these data has been so far undertaken solely within the framework of linear elasticity, neglecting the porous nature of gels. We investigate in this work the deformation of a thick poroelastic layer with surface tension subjected to an arbitrary distribution of time-dependent axisymmetric surface forces. Following the derivation of a general analytical solution, we then focus on the specific problem of a liquid drop sitting on a soft poroelastic substrate. We investigate how the deformation and the solvent concentration field evolve in time for various droplet sizes. In particular, we show that the ridge height beneath the triple line grows logarithmically in time as the liquid migrates toward the ridge. We then study the relaxation of the ridge following the removal of the drop and show that the drop leaves long-lived footprints after removal which may affect surface and wetting properties of gel layers and also the motion of living cells on soft materials. Preliminary experiments performed with water droplets on soft PDMS gel layers are in excellent agreement with the theoretical predictions.

Diffusiophoretic manipulation of particles in a drop deposited on a hydrogel.

We report an experimental study on the manipulation of colloidal particles in a drop sitting on a hydrogel. The manipulation is achieved by diffusiophoresis, which describes a directed motion of particles induced by solute gradients. By letting the solute concentrations for the drop and the hydrogel be different, we control the motion of particles in a stable suspension, which is otherwise difficult to achieve. We show that diffusiophoresis can cause the particles to move either toward or away from the liquid-air interface depending on the direction of the solute gradient and the surface charge of the particles. We measure the particle adsorption experimentally and rationalize the results with a one-dimensional numerical model. We show that diffusiophoretic motion is significant at the lengthscale of a drop deposited on a hydrogel, which suggests a simple method for the deposition of particles on hydrogels.

Tuning the Receding Contact Angle on Hydrogels by Addition of Particles.

Control of the swelling, chemical functionalization, and adhesivity of hydrogels are finding new applications in a wide range of material systems. We investigate experimentally the effect of adsorbed particles on hydrogels on the depinning of contact lines. In our experiments, a water drop containing polystyrene microspheres is deposited on a swelling hydrogel, which leads to the drop absorption and particle deposition. Two regimes are observed: a decreasing drop height with a pinned contact line followed by a receding contact line. We show that increasing the particles concentration increases the duration of the first regime and significantly decreases the total absorption time. The adsorbed particles increase the pinning force at the contact line. Finally, we develop a method to measure the receding contact angle with the consideration of the hydrogel swelling.

A liquid contact line receding on a soft gel surface: dip-coating geometry investigation.

We studied the dynamics of a liquid contact line receding on a hydrophobic soft gel (SBS-paraffin). In order to realize a well-defined geometry with an accurate control of velocity, a dip-coating setup was implemented. Provided that the elastic modulus is small enough, a significant deformation takes place near the contact line, which in turn drastically influences the wetting behaviour. Depending on the translation velocity of the substrate, the contact line exhibits different regimes of motions. Continuous motions are observed at high and low velocities, meanwhile two types of stick-slip motion - periodic and erratic - appear at intermediate velocities. We suggest that the observed transitions could be explained in terms of the competition between different frequencies, i.e., the frequency of the strain field variation induced by the contact line motion and the crossover frequency of the gel related to the material relaxation. Our results provide systematic views on how the wetting of liquid is modified by the rheological properties of a complex soft substrate.

Evaporation of a sessile droplet: inside the coffee stain.

We have investigated experimentally, for the first time at microscopic level, the growth of the deposit left around a drop of colloids drying on a solid surface ("coffee stain effect"). Direct observations show that there are several distinct phases of growth, the later ones exhibiting surprising pattern formations with spatial modulation of the deposit. In addition, fluorescence reveals that the initial growth phase is governed by a single length scale, increasing with time as t(23). We show that this exponent is a direct consequence of the divergence of evaporation near contact line evidenced by Deegan et al. We propose a simple ballistic model that allows us to calculate both this exponent and the prefactor, in agreement with yet available more complex descriptions. This model also opens the possibility to include effects neglected up to now.

Straight contact lines on a soft, incompressible solid.

The deformation of a soft substrate by a straight contact line is calculated, and the result applied to a static rivulet between two parallel contact lines. The substrate is supposed to be incompressible (Stokes-like description of elasticity), and having a non-zero surface tension, that eventually differs depending on whether its surface is dry or wet. For a single straight line separating two domains with the same substrate surface tension, the ridge profile is shown to be very close to that of Shanahan and de Gennes, but shifts from the contact line of a distance equal to the elastocapillary length built upon substrate surface tension and shear modulus. As a result, the divergence near contact line disappears and is replaced by a balance of surface tensions at the contact line (Neumann equilibrium), though the profile remains nearly logarithmic. In the rivulet case, using the previous solution as a Green function allows one to calculate analytically the geometry of the distorted substrate, and in particular its slope on each side (wet and dry) of the contact lines. These two slopes are shown to be nearly proportional to the inverse of substrate surface tensions, though the respective weight of each side (wet and dry) in the final expressions is difficult to establish because of the linear nature of standard elasticity. A simple argument combining Neumann and Young equations is however provided to overcome this limitation. The result may have surprising implications for the modelling of hysteresis on systems having both plastic and elastic properties, as initiated long ago by Extrand and Kumagai.

Gyroscopic instability of a drop trapped inside an inclined circular hydraulic jump.

A drop of moderate size deposited inside a circular hydraulic jump remains trapped at the shock front and does not coalesce with the liquid flowing across the jump. For a small inclination of the plate on which the liquid is impacting, the drop does not always stay at the lowest position and oscillates around it with a sometimes large amplitude, and a frequency that slightly decreases with flow rate. We suggest that this striking behavior is linked to a gyroscopic instability in which the drop tries to keep constant its angular momentum while sliding along the jump.

Coexistence of two singularities in dewetting flows: regularizing the corner tip.

Entrainment in wetting and dewetting flows often occurs through the formation of a corner with a very sharp tip. This corner singularity comes on top of the divergence of viscous stress near the contact line, which is only regularized at molecular scales. We investigate the fine structure of corners appearing at the rear of sliding drops. Experiments reveal a sudden decrease of tip radius, down to 20 microm, before entrainment occurs. We propose a lubrication model for this phenomenon, which compares well to experiments. Despite the disparity of length scales, it turns out that the tip size is set by the classical viscous singularity, for which we deduce a nanometric length from our macroscopic measurements.

Meandering rivulets on a plane: a simple balance between inertia and capillarity.

Experiments on streams of water flowing down a rigid substrate have been performed for various plate inclinations and flow rates, and we focused on the regime of stationary meanders. The outcome is that (i) the flow is highly hysteretic--the shape of the meanders varies with flow rate only for increasing flow rates, and the straight rivulet regime does not appear for decreasing flow rate, and (ii) a simple force balance, including inertia, capillary forces, and also hysteresis of wetting, accounts well for the experimental instability threshold flow rate and for the final radius of curvature of the meanders.

Defects and spatiotemporal disorder in a pattern of falling liquid columns.

Disordered regimes of a one-dimensional pattern of liquid columns hanging below an overflowing circular dish are investigated experimentally. The interaction of two basic dynamical modes (oscillations and drift) combined with the occurrence of defects (birth of new columns, disappearances by coalescences of two columns) leads to spatiotemporal chaos. When the flow rate is progressively increased, a continuous transition between transient and permanent chaos is pointed into evidence. We introduce the rate of defects as the sole relevant quantity to quantify this "turbulence" without ambiguity. Statistics on both transient and endlessly chaotic regimes enable to define a critical flow rate around which exponents are extracted. Comparisons are drawn with other interfacial pattern-forming systems, where transition towards chaos follows similar steps. Qualitatively, careful examinations of the global dynamics show that the contamination processes are nonlocal and involve the propagation of blocks of elementary laminar states (such as propagative domains or local oscillations), emitted near the defects, which turn out to be essential ingredients of this self-sustained disorder.