RESUMEN
Frictional network formation has become a new paradigm for understanding the non-Newtonian shear-thickening behavior of dense suspensions. Recent studies have exclusively focused on interparticle friction that instantaneously vanishes when applied shear is ceased. Herein, we investigate a friction that emerges from dynamic chemical bridging of functionalized particle surfaces sheared into close proximity. This enables tailoring of both friction magnitude and the time release of the frictional coupling. The experiments use dense suspensions of thiol-functionalized particles suspended in ditopic polymers endcapped with benzalcyanoacetamide Michael-acceptors. The subsequent room temperature, catalyst-free dynamic thia-Michael reactions can form bridging interactions between the particles with dynamic covalent bonds that linger after formation and release in the absence of shear. This chemical friction mimics physical friction but is stickier, leading to tunable rheopexy. The effect of sticky friction on dense suspension rheology is explored by varying the electronic nature of the benzalcyanoacetamide moiety, the molecular weight of the ditopic polymers, the amount of a competitive bonding compound, and temperature. These results demonstrate how dynamic-bond-induced sticky friction can be used to systematically control the time dependence of the non-Newtonian suspension rheology.
RESUMEN
The application of stress can drive a dense suspension into a regime of highly non-Newtonian response, characterized by discontinuous shear thickening (DST) and potentially shear jamming (SJ), due to the formation of a frictionally stabilized contact network. Investigating how the molecular weight of the suspending solvent affects the frictional particle-particle interactions, we report on experiments with suspensions of fumed silica particles in polyethylene glycol (PEG). Focusing on the monomer-to-oligomer limit, with n = 1 to 8 ethylene oxide repeat units, we find that increasing n enhances shear thickening under steady-state shear and even elicits rapidly propagating shear jamming fronts, as assessed by high-speed ultrasound imaging of impact experiments. We associate this behavior with a weakening of the solvation layers surrounding the particles as n is increased, which thereby facilitates the formation of frictional contacts. We argue that for n larger than the monomer-to-oligomer limit the trend reverses and frictional interactions are diminished, as observed in prior experiments. This reversal occurs because the polymeric solvent transitions from being enthalpically bound to entropically bound to the particle surfaces, which strengthens solvation layers.