On the rheology of pendular gels and morphological developments in paste-like ternary systems based on capillary attraction

We investigate capillary bridging-induced gelation phenomena in silica particle suspensions and pastes, where a particle-wetting fluid is added as the third component. Increasing the wetting fluid loading in the ternary system induces a morphological transition from a pendular network to compact capillary aggregates network, with an intermediate funicular state. To our knowledge, the formation of percolated structures from compact capillary aggregates when the volume fraction of a wetting fluid approaches that of the particles is unprecedented. Such structures appear to result from the arrested coalescence of compact capillary aggregates due to the balance between the Laplace pressure and solid-like properties (yield stress, elasticity) of the aggregates. Shear-induced yielding of the ternary systems, linked to their percolating nature, is strongly influenced by the amount of wetting fluid phase. A non-monotonic dependence of the yield stress on the amount of wetting fluid is found, with the maximum yield stress obtained for a wetting fluid-to-particle volume fraction ratio of 0.2-0.3. For pendular systems, linear viscoelastic properties display a soft glassy rheological behavior above the percolation threshold (around 4 vol% particles), and complex viscosity data can be scaled using the high frequency plateau value, as well as a single characteristic relaxation time, which decreases when the particle concentration is increased. In addition, the particle concentration dependence of the yielding transition in the pendular regime appears to be efficiently described by two parameters extracted from the steady state flow curves: the yield stress and the limiting viscosity at a high shear rate. Although these non-colloidal networks result from flow-driven assembly, the scaling laws for our pendular gels are reminiscent of colloidal gels with a fractal geometry. Our studies pinpoint new pathways to create physical gels where the interparticle attraction strength is determined by capillary interactions.