Molecular Friction Mechanisms Across Nanofilms of a Bilayer-Forming Ionic Liquid.
The prevailing paradigm in boundary lubrication asserts, in essence, that surfaces coated in amphiphiles slide past each other by way of the "slippery" exposed alkyl chains while the polar head group remains anchored at the surface. Here we show, for ionic liquid boundary lubricants, that the molecular mechanism of shearing is more subtle; while a monolayer on each surface gives rise to alkyl plane shearing, a bilayer on each surface shears at the ionic (nonalkyl) interface. The incorporation of water from the environment dramatically alters the shear at ionic interfaces but leaves alkyl plane shearing unaffected. Our experiments involve shearing two identical and atomically smooth surfaces past one another with films of an ionic liquid between, with subnanometer control of the film thickness and ultrasensitive shear stress resolution. With this, we uncover molecular mechanistic details relevant to boundary lubrication in general and the development of ionic liquid lubricants in particular.
†Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
Alexander M
AM
Smith
‡Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
Michael A
MA
Parkes
†Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
Susan
S
Perkin
confinement; ionic liquids; lubrication; nanotribology; shear; surface forces