Generation of defects in model lubricant monolayers and their contribution to energy dissipation in friction

Abstract

The structural, mechanical (friction) and spectroscopic properties of model lubricant films made of self-assembled and Langmuir–Blodgett monolayers on quartz, mica and gold have been investigated with atomic force microscopy, the surface forces apparatus and sum-frequency generation. In these films, the molecules tend to form densely packed structures, with the alkane chains mostly vertical and parallel to each other. The SFG results suggest that under moderate pressures of a few tens of MPa, the methyl end group of the alkane chains is rotated to accommodate a terminal gauche distortion. The molecule, however, retains its upright close-packed structure with a lattice periodicity when ordered, which can be resolved by AFM. At pressures above 0.1 GPa, changes in the form of collective molecular tilts take place that lower the height of the monolayer. Only certain angles of tilt are allowed that are explained by the interlocking of methylene units in neighboring chains. The discrete angular tilts are accompanied by increases in friction. A model based on the van der Waals attractive energy between chains is used to explain the stability of the films and to estimate the cohesive energy changes during tilt and, from that, the increases in friction force.