Geocolloidal interactions and relaxation dynamics under nanoconfinement: Effects of salinity and particle concentration

[Display omitted] Energy-related contaminants are frequently associated with geocolloids that translocate in underground fissures with dimensions comparable with geocolloids. To assess the transport and impact of energy-related contaminants in geological systems, fundamental understandings of interfacial behaviors of nanoparticles under confinement is imperative. We hypothesize that the dynamic properties of geocolloids, as well as their dependence on aqueous medium conditions would deviate from bulk behaviors under nanoconfinement. Force profiles and rheological properties of 50 nm silica nanoparticles in aqueous media confined between mica surfaces as a function of surface separation, particle concentrations, and salinity were measured utilizing the surface forces apparatus. Force profiles revealed the critical surface separation for nonlinear rheological behaviors coincides with the onset of exponential repulsion between mica surfaces. When salts were absent, the normal forces and viscosity values of colloidal suspensions resembled pure water. In contrast, with salts, the force profiles and corresponding critical length scales were found to be highly sensitive to the particle concentration and the degree of confinement. A Newtonian to shear-thinning transition was captured with increasing degrees of confinement. Our results show that the interplay among confinement, particle, and ionic concentrations can alter the interparticle forces and rheological responses of true nanosized-colloidal suspensions and thus their transport behaviors under nanoconfinement for the first time.