The dynamics of polymer bridge formation and disruption and its effect on the bulk rheology of suspensions.

Bridge-flocculated colloidal gels are used in many important processes and products such as gel casting for advanced ceramics, precursor inks for 3D printing, and waste treatment strategies. An important aspect of polymer bridged gels that makes them excellent candidates for these applications is the precise control it affords for control of rheological properties. Recent studies have shown that adhesion between bridged surfaces increases with time as the number of polymer bridges formed grows. However, the consequences of the dynamics of these processes toward bulk rheological properties have not been studied. Here we investigate the link between the dynamics of polymer bridging and disruption and bulk rheology in dense colloidal silica particle suspensions flocculated by polyethylene oxide (PEO). Microscale pull-off force measurements using atomic force microscope (AFM) show that upon repeated disruption and establishment of bridged contact, the adhesion between the surfaces is reduced. During contact disruption, the polymer chains bridging the two surfaces are stretched leading to chain scission. On the re-establishment of contact, these fragmented polymer chains are unable to fully re-establish the adhesion. Macroscale measurements using oscillatory rheology show that this reduced adhesion results in reduction of both the storage modulus and the yield stress. If the slurry is subjected to high shear for long periods, polymer chain scission is amplified, and the fragmented polymer chains are unable to bridge the particles again, resulting in free-flowing slurries.