Complexity in Wetting Dynamics.

The spreading dynamics of a droplet of pure liquid deposited on a rigid, nonsoluble substrate has been extensively investigated. In a purely hydrodynamic description, the dynamics of the contact line is determined by a balance between the energy associated with the capillary driving force and the energy dissipated by the viscous shear in the liquid. This balance is expressed by the Cox-Voinov law, which relates the spreading velocity to the contact angle. More recently, complex situations have been examined in which dissipation and/or the driving force may be strongly modified, leading to sometimes spectacular changes in wetting dynamics. We review recent examples of effects at the origin of deviations from the hydrodynamic model, which may involve physical or chemical modifications of the substrate or of the wetting liquid, occurring at scales ranging from the molecular to the mesoscopic.

How emulsified droplets induce the bursting of suspended films of liquid mixtures.

Emulsion droplets of silicone oil (PDMS) are widely used as antifoaming agents but, in the case of non-aqueous foams, the mechanisms responsible for the bursting of the films separating the bubbles remain unclear. We consider a ternary non-aqueous liquid mixture in which PDMS-rich microdroplets are formed by spontaneous emulsification. In order to quantitatively assess the effect of the emulsified microdroplets, we measure the lifetime of sub-micrometer-thick suspended films of these emulsions as well as the time variations of their thickness profiles. We observe that a droplet entering the film reduces its lifetime by inducing a local and fast thinning. In most cases, we ascribe it to the spreading of the drop at one of the film interfaces with air, which drags the underlying liquid and eventually causes the film to burst rapidly. We explain why, despite slower spreading, more viscous droplets cause films to burst more efficiently. More rarely, microdroplets may bridge the two interfaces of the film, resulting in an even more efficient bursting of the film, which we explain.

Drying Liquid Coatings with an Evaporation Mask: Theory and Experiments.

We report a study of the spatially varying thickness of dried films of polymer solutions resulting from a nonuniform evaporation flux. The controlled heterogeneity of the evaporation flux is imposed by placing a solid mask above the evaporating film spread on a solid substrate. At the end of drying, a depression has formed under the mask, together with overthicknesses extending from the edge of the mask and over distances that may be larger than its size. By considering the flows induced in a vertically homogeneous film, we obtain analytical solutions for the thickness profiles during drying using a linear approximation in the limits of either gravity or capillarity-driven flows. We demonstrate that gravity can play a role in the deformations of the films, even if their initial thicknesses are 1 order of magnitude smaller than the capillary length. In addition, we examine two possible reference states for the linear approximation, i.e., far from the mask in the film of decreasing thickness and increasing viscosity, or under the mask where no evaporation occurs. We further compare these results with experimental ones obtained by drying thin films of polymer solutions under a mask. Both the extent and amplitude of the thickness heterogeneities of the dry film are quantitatively predicted by the linear analysis for a reference state under the mask. Our results therefore provide new insight on the patterns resulting from evaporation masks and can be generalized to minimize thickness heterogeneities in any situation in which the evaporation flux is nonuniform.

Formation of glassy skins in drying polymer solutions: approximate analytical solutions.

We study the formation of a glassy skin at the air interface of drying polymer solutions. We introduce a simple approximation, which is valid for most diffusion problems, and which allows us to derive analytical relationships for the polymer concentration as a function of time. We show that the approximate results differ by less than 15% from those obtained by numerically solving the diffusion equation. We use the approximation to study skin formation in evaporating solutions. We focus on the influence of variations of the mutual diffusion coefficient with concentration, when the latter decreases sharply at high concentrations, as observed in the vicinity of the glass transition. We show that the skin thickness depends very strongly on the exponent characterising the decrease of the diffusion coefficient, in contrast to the polymer volume fraction at the interface, which varies only slightly with the exponent.

Uptake kinetics of spontaneously emulsified microdroplets at an air-liquid interface.

Understanding the transfers occurring at the interfaces between emulsions and air is required to predict the properties of foamed emulsions, used for example as antifoaming lubricants or for oil extraction. Whereas bubbling oil-in-water emulsions have been studied in details, oil-in-oil emulsions have received less attention. We consider a phase-separating mixture of three oils being Polydimethylsiloxane (PDMS), decane and cyclopentanol. PDMS is dispersed as submicrometer-sized droplets by spontaneous emulsification. In bulk, we show that the time evolution of the emulsion is driven by undelayed coalescence of the Brownian microdroplets. At the freshly created interface of an air bubble created in the emulsion, we use tensiometry measurements to investigate the uptake kinetics of PDMS-rich microdroplets at the air-liquid interface. Specifically, we evidence two mechanisms of uptake: the advection of droplets at the interface during bubble swelling, followed by their diffusion on a longer time scale. We model the growth of the PDMS-rich layer at the interface and, finally, we establish the surface energy of a thin film of PDMS-rich phase squeezed between air and liquid as a function of its thickness.

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.

Water film squeezed between oil and solid: drainage towards stabilization by disjoining pressure.

The spontaneous drainage of aqueous solutions of salt squeezed between an oil drop and a glass surface is studied experimentally. The thickness profile of the film is measured in space and time by reflection interference microscopy. As the film thins down, three regimes are identified: a capillary dominated regime, a mixed capillary and disjoining pressure regime, and a disjoining pressure dominated regime. These regimes are modeled within the lubrication approximation, and the role of the disjoining pressure is precisely investigated in the limit of thicknesses smaller than the range of electrostatic interactions. We derive simple analytical laws describing the drainage dynamics, thus providing tools to uncouple the effect of the film geometry from the effects of the disjoining or capillary pressures.

Understanding the role of molar mass and stirring in polymer dissolution.

When a dry soluble polymer is put in contact with a large quantity of solvent, it swells and forms a transient gel, and eventually, yields a dilute solution of polymers. Everyday lab experience shows that when the molar mass is large, namely tens of times larger than entanglement mass, this dissolution process is slow and difficult and may require stirring. Here, in agreement with previous results, we found that the time needed to turn a dry grain into a dilute solution is not limited by water diffusion in the glassy or semi-crystalline dry polymer, but rather by the life-time of the transient gel made of entangled chains. In addition, we shed new light on the dissolution process by demonstrating that, in contrast to theoretical predictions, the gel life-time is not governed by reptation. We show instead that swelling is simply controlled by the osmotic pressure and the gel permeability until the overlap concentration is reached within the gel. At this stage, the gel turns into a dilute solution in which polymers are dispersed by natural convection. The observed dependence of the dissolution process on the molar mass therefore originates from the molar mass dependent overlap concentration. Under stirring, or forced convection, the polymer gel disappears at a higher critical concentration that depends on the shear rate. We suggest a description of the experimental data which uses the rheological flow curves of the solutions of the considered polymer. Inversely, dissolution times of polymer powders under stirring can be inferred from classical rheological measurements of the polymer solutions at varied concentrations.

Wetting of polymers by their solvents.

We review the studies on the wetting of soluble polymeric substrates by their solvents, both in the literature and conducted in our group in the past decade. When a droplet of solvent spreads on a soluble polymer layer, its wetting angle can strongly vary with the contact line velocity even at capillary numbers smaller than unity, in contrast to non-soluble substrates. The solvent content in the polymer is a key parameter for the spreading dynamics; that content is set by the initial conditions, but also by the transfers occurring from the droplet to the polymer layer during spreading. We focus on hydrophilic amorphous polymers that are glassy at room temperature, and we discuss the consequences on wetting of the very large changes in the polymer physical properties induced by solvent sorption. We finally present new results on polymers of varying molar masses, and show how they open new perspectives for a better understanding of powder dissolution.

Glass transition accelerates the spreading of polar solvents on a soluble polymer.

We study the wetting of polymer layers by polar solvents. As previously observed, when a droplet of solvent spreads, both its contact angle and velocity decrease with time as a result of solvent transfers from the droplet to the substrate. We show that, when the polymer is initially glassy, the angle decreases steeply for a given value of the velocity, Ug. We demonstrate that those variations result from a plasticization, i.e., a glass transition, undergone by the polymer layer during spreading, owing to the increase of its solvent content. By analyzing previous predictions on the wetting of rigid and soft viscoelastic substrates, we relate Ug to the viscosity of the polymer gel close to the glass transition. Finally, we derive an analytical prediction for Ug based on existing predictions for the water transfer from the droplet to the substrate. Using polar solvents of different natures, we show that the experimental data compare well to the predicted expression for Ug.

Dynamic wetting on a thin film of soluble polymer: effects of nonlinearities in the sorption isotherm.

The wetting dynamics of a solvent on a soluble substrate interestingly results from the rates of the solvent transfers into the substrate. When a supported film of a hydrosoluble polymer with thickness e is wet by a spreading droplet of water with instantaneous velocity U, the contact angle is measured to be inversely proportionate to the product of thickness and velocity, eU, over two decades. As for many hydrosoluble polymers, the polymer we used (a polysaccharide) has a strongly nonlinear sorption isotherm φ(a(w)), where φ is the volume fraction of water in the polymer and aw is the activity of water. For the first time, this nonlinearity is accounted for in the dynamics of water uptake by the substrate. Indeed, by measuring the water content in the polymer around the droplet φ at distances as small as 5 µm, we find that the hydration profile exhibits (i) a strongly distorted shape that results directly from the nonlinearities of the sorption isotherm and (ii) a cutoff length ξ below which the water content in the substrate varies very slowly. The nonlinearities in the sorption isotherm and the hydration at small distances from the line were not accounted for by Tay et al., Soft Matter 2011, 7, 6953. Here, we develop a comprehensive description of the hydration of the substrate ahead of the contact line that encompasses the two water transfers at stake: (i) the evaporation-condensation process by which water transfers into the substrate through the atmosphere by the condensation of the vapor phase, which is fed by the evaporation from the droplet itself, and (ii) the diffusion of liquid water along the polymer film. We find that the eU rescaling of the contact angle arises from the evaporation-condensation process at small distances. We demonstrate why it is not modified by the second process.

Correction: Developing an advanced gut on chip model enabling the study of epithelial cell/fibroblast interactions.

Correction for 'Developing an advanced gut on chip model enabling the study of epithelial cell/fibroblast interactions' by Marine Verhulsel et al., Lab Chip, 2021, 21, 365-377, https://doi.org/10.1039/d0lc00672f.

Spinodal stratification in micellar films between oil and silica.

We report on the thinning mechanisms of supported films of surfactant (nTAB) solutions above the critical micellar concentration. The films are formed by pressing an oil drop immersed in an aqueous surfactant solution on a silica surface. Depending on the length of the carbon chain of the surfactant and its concentration, two modes of destabilization of the stratified films are observed. The first one proceeds by heterogeneous nucleation, characterized by the lateral expansion of the domain of lower thickness as evidenced long ago in suspended micellar films. In addition, the simultaneous stepwise thinning of several domains, called spinodal stratification, is observed here in supported films. We measure the time evolution of the thickness of the films, and we discuss the selection mechanism of each destabilization mode.

Developing an advanced gut on chip model enabling the study of epithelial cell/fibroblast interactions.

Organoids are widely used as a model system to study gut pathophysiology; however, they fail to fully reproduce the complex, multi-component structure of the intestinal wall. We present here a new gut on chip model that allows the co-culture of primary epithelial and stromal cells. The device has the topography and dimensions of the mouse gut and is based on a 3D collagen I scaffold. The scaffold is coated with a thin layer of laminin to mimic the basement membrane. To maintain the scaffold structure while preserving its cytocompatibility, the collagen scaffold was rigidified by threose-based post-polymerization treatment. This treatment being cytocompatible enabled the incorporation of primary intestinal fibroblasts inside the scaffold, reproducing the gut stromal compartment. We observed that mouse organoids, when deposited into crypts, opened up and epithelialized the scaffold, generating a polarized epithelial monolayer. Proper segregation of dividing and differentiated cells along the crypt-villus axis was achieved under these conditions. Finally, we show that the application of fluid shear stress allows the long-term culture of this intestinal epithelium. Our device represents a new biomimetic tool that captures key features of the gut complexity and could be used to study gut pathophysiology.

Aggregation behavior of two spheres falling through an aging fluid.

We study the behavior of two spheres that settle along their line of center in a yield stress fluid that "ages:" a Laponite suspension. In such a fluid, the fluid flow behind a falling single particle can either exhibit a negative wake, i.e., an upward motion, or not, according to the stress exerted by the particle on the fluid. We show that, if their initial separation distance is smaller than 15 radii, two identical particles cluster whatever the wake's structure. In addition, in the conditions within which a negative wake is observed, we evidence an unexpected lateral motion of the spheres.

Surface fluctuations of liquids confined on flat and patterned solid substrates.

We report experimental measurements of the surface fluctuations of micron-thick oil films spread onto a solid substrate. We use a recently developed optical technique based on the measurement of the deflection of a laser beam triggered by changes in the local surface slope. When the liquid is spread on a flat substrate, fluctuation dynamics slow down as the thickness is decreased, in quantitative agreement with previous predictions. In addition, we investigate the consequences on surface fluctuations of the patterning of the substrate with a rectangular grating. For liquid film thicknesses smaller than the typical wavelength probed, we demonstrate that surface fluctuations are modified by the underlying pattern: The shape of the fluctuation spectra varies periodically with the spatial position over the pattern and, in addition, the fluctuations become locally anisotropic. However, the spatially averaged spectrum is isotropic.

Two beam surface fluctuation specular reflection spectroscopy.

In surface fluctuation specular reflection spectroscopy (SFSRS) deflections of a specularly reflected laser beam are used to characterize thermally excited surface waves. Here we report on a new two beam version of SFSRS in which the deflections of two reflected laser beams from separate locations on a surface are correlated. We demonstrate that this new two beam SFSRS technique can be used to determine directly the power spectrum of height fluctuation of thermally excited surface waves over a large range of both frequencies and wavevectors. In addition, we show that the technique is well suited for materials ranging from simple liquids to complex liquids and soft solids, including turbid materials.

Retarded transfers of an emulsified two-component oil phase.

We study oil evaporation from oil in water emulsions, whose oil phases are mixtures of two alkanes of different solubilities in water. The aqueous phase is a colloidal clay suspension that exhibits a yield stress, in which the oil droplets are immobilized. A surfactant-free emulsion is thus formed, providing a convenient model system in which the oil transfer solely occurs through the aqueous phase. When the emulsion is left in contact with the atmosphere, oil evaporation results in the formation of a droplet-free region in the emulsion, and that region grows diffusively with time. We show that the transfer of the more soluble alkane is dramatically retarded when the mixture ratio of the less soluble alkane is increased, as a consequence of entropy loss associated with oil demixing. Using a simple transfer model, which captures well the experimental trends, we study the alkane concentrations both within the oil droplets and within the aqueous phase of the emulsion. We report overshoots in the concentration profiles of the less soluble alkane both in the emulsion and in the droplets, and explain their formation using a qualitative argument.

Boiling of an emulsion in a yield stress fluid.

We report the boiling behavior of pentane emulsified in a yield stress fluid, a colloidal clay (Laponite) suspension. We have observed that a superheated state is easily reached: the emulsion, heated more than 50 °C above the alkane boiling point, does not boil. Superheating is made possible by the suppression of heterogeneous nucleation in pentane, resulting from the emulsification process, a phenomenon evidenced decades ago in studies of the superheating of two phase fluids. We have furthermore studied the growth of isolated bubbles nucleated in the emulsion. The rate of increase of the bubble radius with time depends on both the temperature and emulsion volume fraction but, rather unexpectedly, does not depend on the fluid rheology. We show that the bubbles grow by diffusion of the alkane through the aqueous phase between liquid droplets and bubbles, analogously to an Ostwald ripening process. The peculiarity of the process reported here is that a layer depleted in oil droplets forms around the bubble, layer to which the alkane concentration gradient is confined. We successfully describe our experimental results with a simple transfer model.