Frédéric Doumenc

Stick−Slip Patterning at Low Capillary Numbers for an Evaporating Colloidal Suspension

Pattern formation from a silica colloidal suspension that is evaporating has been studied when a movement is imposed to the contact line. This article focuses on the stick-slip regime observed for very low contact line velocities. A capillary rise experiment has been specially designed for the observation and allows us to measure the pinning force that increases during the pinning of the contact line on the growing deposit. We report systematic measurements of this pinning force and derive scaling laws when the velocity of the contact line, the colloid concentration, and the evaporation rate are varied. Our analysis supports the idea that the pinning of the contact line results from a competition between the geometry of the growing deposit and the force due to gravity.

Transient Rayleigh-Benard-Marangoni Convection due to Evaporation : a Linear Non-normal Stability Analysis

The convective instability in a plane liquid layer with time-dependent temperature profile is investigated by means of a general method suitable for linear stability analysis of an unsteady basic flow. The method is based on a non-normal approach, and predicts the onset of instability, critical wavenumber and time. The method is applied to transient Rayleigh–Benard–Marangoni convection due to cooling by evaporation. Numerical results as well as theoretical scalings for the critical parameters as function of the Biot number are presented for the limiting cases of purely buoyancy-driven and purely surface-tension-driven convection. Critical parameters from calculations are in good agreement with those from experiments on drying polymer solutions, where the surface cooling is induced by solvent evaporation.

Drying of a solution in a meniscus: a model coupling the liquid and the gas phases.

A model simulating the drying of a solution in a meniscus in contact with a moving substrate is developed. It takes into account the hydrodynamics in the solution in the framework of the lubrication approximation, the vapor diffusion in the gas phase, and the variation of physical properties during drying. The free surface profile and spatial evaporation flux are not imposed a priori but result from the simulation of the mass transfer in the liquid/gas system (1.5-sided model). Several regimes are observed depending on the substrate velocity. For a large substrate velocity, the classical Landau-Levich regime is obtained. For smaller velocities, a drying front appears that is characterized by a strong concentration gradient and a peak in the evaporation flux. The coupling between the evaporation flux and the meniscus shape in this regime is analyzed. Another regime appears at a very low substrate velocity and seems to be driven by a competition between advection and diffusion. This macroscopic model simulates recent experimental results, namely, the dependence of the deposit thickness on the substrate velocity, which scales as 1/V in the regime dominated by evaporation.

Drying of colloidal suspensions and polymer solutions near the contact line: deposit thickness at low capillary number.

Drying experiments with a receding contact line have been performed with silica colloidal suspensions and polyacrylamide (PAAm) polymer solutions. The experimental setup allows to control the receding movement of the contact line and the evaporation flux separately. Deposit thickness as a function of these two control parameters has been investigated. The different systems exhibit a similar behavior: in the regime of very low capillary numbers the deposit thickness scaled by the solute volume concentration and the evaporation rate is proportional to the inverse of the contact line velocity. Both the scaling exponent and the constant (which has the dimension of a length) do not depend on the system under study. The observation of this evaporative regime confirms some recent results obtained by Le Berre et al. on a very different system (phospholipidic molecules) and fully supports their interpretation. Following their approach, a simple model based on mass balance accounts for these results. This implies that this regime is dominated by the evaporation and that the deformation of the meniscus induced by viscous forces does not play any significant role. When increasing the velocity, another regime is observed where the thickness does not depend significantly on the velocity.

Self-patterning induced by a solutal Marangoni effect in a receding drying meniscus

This paper examines through numerical simulations the impact of a solutal Marangoni effect on the deposit obtained from a polymer solution. A hydrodynamical model with lubrication approximation is used to describe the liquid phase in a dip-coating–like configuration. The studied case considers evaporation in stagnant air (diffusion-limited evaporation), which results in a coupling between the liquid and gas phases. Viscosity, surface tension, and saturated vapor pressure depend on the solute concentration. In the evaporative regime, when the surface tension increases with the polymer concentration, the Marangoni effect induces a periodic regime. This results in a self-organized periodic patterning of the dried film in certain control parameter ranges. A morphological phase diagram as well as meniscus and dry-deposit shapes are provided as a function of the substrate velocity and bulk solute concentration.

Transient Rayleigh-Bénard-Marangoni solutal convection

Solutal driven flow is studied for a binary solution submitted to solvent evaporation at the upper free surface. Evaporation induces an increase in the solute concentration close to the free surface and solutal gradients may induce a convective flow driven by buoyancy and/or surface tension. This problem is studied numerically, using several assumptions deduced from previous experiments on polymer solutions. The stability of the system is investigated as a function of the solutal Rayleigh and Marangoni numbers, the evaporative flux and the Schmidt number. The sensitivity of the thresholds to initial perturbations is analyzed. The effect of viscosity variation during drying is also investigated. At last numerical simulations are presented to study the competition between buoyancy and Marangoni effects in the nonlinear regime.

Analysis of the solvent diffusion in glassy polymer films using a set inversion method

Abstract Within the framework of solvent diffusion in glassy polymers, this paper concerns an experimental study of toluene sorption and desorption in P(MMA/nBMA) copolymer films. Gravimetric experiments (quartz microbalance) are performed in a pressure and temperature controlled chamber. Coupling between solvent diffusion and viscoelastic relaxation is taken into account through the time-dependent solubility model, based on the Fick diffusion equation inside the film and a time variable boundary condition at the film/vapor interface. Viscoelastic relaxation is described by a first order model or by a stretched exponential. In the present paper, a special focus is given on the set inversion method used to analyze the data and to derive well-defined uncertainty intervals upon each determined quantity, taking all the uncertainties on the weight measurements into account. We find that the mutual diffusion coefficient strongly decreases in the glassy state, of about two orders of magnitude for a 0.05 decrease in the solvent weight fraction.

Physical aging of glassy PMMA/toluene films: Influence of drying/swelling history

Gravimetry experiments in a well-controlled environment have been performed to investigate aging for a glassy PMMA/toluene film. The temperature is constant and the control parameter is the solvent vapor pressure above the film (i.e. the activity). Several experimental protocols have been used, starting from a high activity where the film is swollen and rubbery and then aging the film at different activities below the glass transition. Desorption and resorption curves have been compared for the different protocols, in particular in terms of the softening time, i.e. the time needed by the sample to recover an equilibrium state at high activity. Non-trivial behaviors have been observed, especially at small activities (deep quench). A model is proposed, extending the Leibler-Sekimoto approach to take into account the structural relaxation in the glassy state, using the Tool formalism. This model well captures some of the observed phenomena, but fails in describing the specific kinetics observed when aging is followed by a short but deep quench.

Can hydrodynamic contact line paradox be solved by evaporation-condensation?

We investigate a possibility to regularize the hydrodynamic contact line singularity in the configuration of partial wetting (liquid wedge on a solid substrate) via evaporation-condensation, when an inert gas is present in the atmosphere above the liquid. The no-slip condition is imposed at the solid-liquid interface and the system is assumed to be isothermal. The mass exchange dynamics is controlled by vapor diffusion in the inert gas and interfacial kinetic resistance. The coupling between the liquid meniscus curvature and mass exchange is provided by the Kelvin effect. The atmosphere is saturated and the substrate moves at a steady velocity with respect to the liquid wedge. A multi-scale analysis is performed. The liquid dynamics description in the phase-change-controlled microregion and visco-capillary intermediate region is based on the lubrication equations. The vapor diffusion is considered in the gas phase. It is shown that from the mathematical point of view, the phase exchange relieves the contact line singularity. The liquid mass is conserved: evaporation existing on a part of the meniscus and condensation occurring over another part compensate exactly each other. However, numerical estimations carried out for three common fluids (ethanol, water and glycerol) at the ambient conditions show that the characteristic length scales are tiny.

Numerical simulation of dip-coating in the evaporative regime

Abstract.A hydrodynamic model is used for numerical simulations of a polymer solution in a dip-coating-like experiment. We focus on the regime of small capillary numbers where the liquid flow is driven by evaporation, in contrast to the well-known Landau-Levich regime dominated by viscous forces. Lubrication approximation is used to describe the flow in the liquid phase. Evaporation in stagnant air is considered (diffusion-limited evaporation), which results in a coupling between liquid and gas phases. Self-patterning due to the solutal Marangoni effect is observed for some ranges of the control parameters. We first investigate the effect of evaporation rate on the deposit morphology. Then the role of the spatial variations in the evaporative flux on the wavelength and mean thickness of the dried deposit is ascertained, by comparing the 2D and 1D diffusion models for the gas phase. Finally, for the very low substrate velocities, we discuss the relative importance of diffusive and advective components of the polymer flux, and consequences on the choice of the boundary conditions.Graphical abstract