Visualization of the Sol-Gel Transition in Porous Networks Using Fluorescent Viscosity-Sensitive Probes.

The sol-gel transition involves the transformation of a colloidal suspension into a system-spanning, interconnected gel. This process is widely used to reinforce mechanically weakened porous artifacts, such as sculptures but the impact of the restricted geometry (porous network) on the gelation dynamics of the solution remains unclear. Here, using fluorescent viscosity-sensitive molecular rotors, confocal microscopy, and model pores, we visualize the local viscosity changes at the microscale that accompany the sol-gel transition of a methyltriethoxysilane solution into a gel network. We show that, with evaporation of the solvent, a viscosity gradient develops near the free surface, triggering the sol-gel transition inside small pores near the surface. In homogeneous porous media, this leads to skin formation, which reduces the evaporation rate. In heterogeneous porous media, a gradient in gel density develops toward the heart of the porous material, where the gel formation mainly occurs as capillary bridges within smaller pores.

Is Unidirectional Drying in a Round Capillary Always Diffusive?

The unidirectional drying of water in cylindrical capillaries has been described since the discovery of Stefan's solution as a vapor diffusion-controlled process with a square root of time kinetics. Here we show that this well-known process actually depends on the way the capillary is closed. Experiments are performed on the evaporation of water in capillaries closed at one end with a solid material or connected to a fluid reservoir. While we recover Stefan's solution in the first case, we show that in the second situation the water plug evaporates at a constant rate with the water-air meniscus remaining pinned at the exit where evaporation proceeds. The presence of the liquid reservoir closing the capillary combined with a capillary pumping effect induces a flow of the water plug toward the evaporation front leading to a constant-rate drying, substantially faster than the prediction of Stefan's equation. Our results show that a transition from a constant-rate evaporation regime at short times to a diffusion-driven evaporation regime at long times can be observed by increasing the viscosity of the fluid in the reservoir blocking the other end of the capillary. Such transition can also be observed by connecting the capillary end to a solidifying fluid like epoxy glue.