Drying of alkoxide gels—Observation of an alternate phenomenology

The process of drying of a porous material as per the current phenomenological theory can be divided into two stages. At first the body shrinks by an amount equal to the volume of liquid that evaporates, and the liquid-vapor interface remains at the exterior surface of the body. The second stage begins when the body becomes too stiff to shrink and the liquid recedes into the interior, leaving air filled pores near the surface. We shall refer to this phenomenology as the drying front model. In our investigation of drying of alkoxide silica gels of less than 50 Angstroms pore radius, we have observed a different drying pattern, in which even after the gel body stops shrinking, drying continues to occur by evaporation on the exterior surface of the gel body, causing spontaneous nucleation of partially or fully dried opaque clusters, randomly distributed in the interior parts of the gel. These clusters than increase in number and size till they coalesce to form an opaque body. Upon further drying, the gel returns to its transparent form. We postulate that this is possible only if the rate of fluid flow in the pores by diffusion is faster than that by Darcy's flow, as well as the evaporation rate at the surface of the gel body. We shall refer to this as the cluster drying model. We shall present results of pin-hole drying experiments on cylindrical alkoxide gels showing that for identical gels the evaporation rate can be increased to change the phenomenology from cluster drying to one that exhibits both phenomenology simultaneously and finally to that of the drying front phenomenology. We shall also show the effect of gel pore size distribution on the phenomenology of drying under identical drying conditions. Finally, we will present evidence that for successful drying of large cylindrical alkoxide gels, drying conditions favoring cluster drying phenomenology is desirable.