Shrinkage and microstructural development during drying of organically modified silica xerogels

We have studied the different driving forces behind syneresis in MTES/TEOS gels by aging them in different H{sub 2}O/EtOH pore fluids. We show using shrinkage, density, contact angle, and N{sub 2} sorption measurements, the influence of gel/solvent interactions on the microstructural evolution during drying. Competing effects of syneresis (that occurs during aging) and drying shrinkage resulted in the overall linear shrinkage of the organically modified gels to be constant at {approximately}50%. Increasing the hydrophobicity of the gels caused the driving force for syneresis to change from primarily condensation reactions to a combination of condensation and solid/liquid interfacial energy. In addition the condensation driven shrinkage was observed to be irreversible, whereas the interfacial free energy driven shrinkage was observed to be partially reversible. Nitrogen sorption experiments show that xerogels with the same overall extent of shrinkage can have vastly different microstructures due to the effects of microphase separation