Nanoconfined ionic liquids: disentangling electrostatic & viscous forces

Abstract

Recent reports of surface forces across nanoconfined ionic liquids have revealed the existence of an anomalously long-ranged interaction apparently of electrostatic origin. Ionic liquids are viscous and therefore it is important to inspect rigorously whether the observed repulsive forces are indeed equilibrium forces or, rather, arise from the viscous force during drainage of the fluid between two confining surfaces. In this paper we present our direct measurements of surface forces between mica sheets approaching in the ionic liquid [C2C1Im][NTf2], exploring three orders of magnitude in approach velocity. Trajectories are systematically fitted by solving the equation of motion, allowing us to disentangle the viscous and equilibrium contributions. First, we find that the drainage obeys classical hydrodynamics with a negative slip boundary condition in the range of the structural force, implying that a nm-thick portion of the liquid in the vicinity of the solid surface is composed of ordered molecules that do not contribute to the flow. Secondly, we show that a long-range static force must indeed be invoked, in addition to the viscous force, in order to describe the data quantitatively. This equilibrium interaction decays exponentially and with decay length is in agreement with the screening length reported for the same system in previous studies. In those studies the decay was simply checked to be independent of velocity and measured at low approach rate, rather than explicitly taking account of viscous effects: we explain why this gives indistinguishable outcomes for the screening length by noting that the viscous force is linear to very good approximation over a wide range of distances.