Linking intermolecular interactions and rheological behaviour in capillary suspensions

Capillary suspensions feature networks of particles connected by liquid bridges, which are obtained by adding a small amount of a second immiscible liquid to a suspension. It is possible to link the network formation as well as the rheological behaviour of capillary suspensions to the intermolecular interactions of their constituents.Through a combination of experimental and numerical methods, we present a novel approach, based on Hansen solubility parameters computed from Molecular Dynamics (MD) simulations, to rationalize and predict the rheological behaviour of capillary suspensions. We investigated the formation of capillary suspensions for various combinations of bulk and secondary liquids mixed with hydrophilic silica particles. The predictions were confirmed experimentally by rheological analysis, interfacial tension measurements and microscopy (CLSM) imaging.Numerical and experimental results show that the Hansen solubility parameters theory allows to predict the formation of capillary suspensions, whose strength exponentially decays with decreasing intermolecular interactions between the secondary liquids and the dispersed particles. High immiscibility between the bulk and secondary liquid strengthens the gel up to a critical immiscibility point, above which the strength of the gel remains mostly affected by the affinity between the secondary liquids and the dispersed particles. Furthermore, we find that hydrogen-bonding and polar interactions control the formation of capillary suspensions. This simple approach can guide the selection of adequate solvents and immiscible secondary liquids, allowing an easy formulation of new particulate-based gels.