Negative intrinsic viscosity in graphene nanoparticle suspensions induced by hydrodynamic slip

Abstract: The viscosity of nanoparticle suspensions is always expected to increase with particle concentration. However, a growing body of experiments on suspensions of atomically thin nanomaterials such as graphene contradicts this expectation. Some experiments indicate effective suspension viscosity values that fall below that of pure solvent at high shear rates and low solid concentrations, i.e., the intrinsic viscosity is negative. To explain this puzzling phenomenon, we combined molecular dynamics and boundary integral simulations to investigate the shear viscosity of few-nanometer graphene sheets in water at high P\'eclet numbers (Pe $> 100$). Our results, covering geometric aspect ratios from 4.5 to 12.0, show robustly that the intrinsic viscosity decreases with increasing aspect ratio and becomes negative beyond a threshold aspect ratio $\approx 5.5$. We demonstrate that this anomalous behavior originates from hydrodynamic slip at the liquid-solid interface, which suppresses particle rotation and promotes stable alignment with the flow direction, thereby reducing viscous dissipation relative to dissipation in pure solvent. This slip mechanism holds for both fully 3D disc-like and quasi-2D particle geometries explored in the molecular simulations. As the concentration of graphene particles increases in the dilute regime, the viscosity initially decreases, falling below that of pure water. At higher concentrations, however, particle aggregation becomes significant, leading to a rise in viscosity after a minimum is reached. These findings confirm the occurrence of a negative intrinsic viscosity in a graphene suspension due only to hydrodynamic effects. Our work has important implications for the design of lubricants, inks, and nanocomposites with tunable viscosity.