Electrotunable Lubrication with Ionic Liquids: the Effects of Cation Chain Length and Substrate Polarity

Electrotunable lubrication with ionic liquids (ILs) provides dynamic control of friction with the prospect to achieve superlubrication. We investigate the dependence of the frictional and structural forces with 1-n,2-methyl-imidazolium tetrafluoroborate [CMIM]⁺[BF₄]^- (n = 2, 4, 6) ILs as a lubricant on the molecular structure of the liquid, normal load, and polarity of the electrodes. Using non-equilibrium molecular dynamics simulations and coarse-grained force-fields, we show that the friction force depends significantly on the chain length of the cation. ILs containing cations with shorter aliphatic chains show lower friction forces, ∼40% for n = 2 as compared to the n = 6 case, and more resistance to squeeze-out by external loads. The normal load defines the dynamic regime of friction, and it determines maxima in the friction force at specific surface charges. At relatively low normal loads, ∼10 MPa, the velocity profile in the confined region resembles a Couette type flow, whereas at high loads, >200 MPa, the motion of the ions is highly correlated and the velocity profile resembles a "plug" flow. Different dynamic regimes result in distinctive slippage planes, located either at the IL-electrode interface or in the interior of the film, which ultimately lead, at high loads, to the observation of maxima in the friction force at specific surface charge densities. Instead, at low loads the maxima are not observed, and the friction is found to monotonously increase with the surface charge. Friction with [CMIM]⁺[BF₄]^- as a lubricant is reduced when the liquid is confined between positively charged electrodes. This is due to better lubricating properties and enhanced resistance to squeeze out when the anion [BF₄]^- is in direct contact with the electrode.