Pore network modeling for evaporation of complex fluids in porous media

Drying of fluids undergoing sol-gel transition in porous media, a process crucial for the consolidation of damaged porous structures in cultural heritage, often leads to skin formation at the surface. This phenomenon significantly hinders evaporation, yet its precise impact on drying kinetics remains poorly understood. To uncover the governing mechanisms, we develop a novel pore network model that closely replicates quasi-two-dimensional experimental porous media in a previous paper [Le Dizès Castell et al., J. Phys. Chem. Lett. 15, 628 (2024)], incorporating spatial gradients in pore size distribution, with smaller pores near the evaporation side. We demonstrate that this pore distribution dictates the air invasion path and extends the constant-rate period of drying in Newtonian liquids, reproducing the experimental drying curves for water. We further extend our model to capture the interplay of capillary-driven liquid flows, space-dependent viscosity increases, and localized skin formation. To incorporate skin formation, we implement a viscosity-dependent vapor pressure rule derived from experimental data on evaporation-induced sol-gel transition within a capillary tube. We identify a simple relationship: vapor pressure decreases once the meniscus fluid viscosity exceeds a critical threshold. By accounting for localized skin formation through reduced evaporation pressure at high-viscosity throats, our model successfully captures the slowdown of drying kinetics, achieving remarkable agreement with experimental drying curve.