Negative Intrinsic Viscosity in Graphene Nanoparticle Suspensions Induced by Hydrodynamic Slip

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 viscosities below that of pure solvent at high shear rates and low solid concentrations, i.e., the intrinsic viscosity is negative. Using molecular dynamics simulations, we investigate the shear viscosity of few-nanometer graphene sheets in water at high Péclet numbers (Pe ≥ 100), for aspect ratios from 4.5 to 12.0. These simulations robustly confirm that the intrinsic viscosity decreases with increasing aspect ratio and becomes negative beyond a threshold ≈5.5, providing a molecular-level confirmation of this behavior in a realistic graphene-water system. Comparison with continuum boundary integral modeling shows quantitative agreement in the dilute regime, confirming the effect is hydrodynamic in origin. 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. Our work has important implications for the design of lubricants, inks, and nanocomposites with tunable viscosity.