The Relationship Between Contact Mechanics and Adhesion in Nanoscale Contacts Between Non-Polar Molecular Monolayers

Atomic and friction force microscopy were employed to examine adhesion and friction between dodecanethiol self-assembled monolayers in pure media as well as in two-component heptane/acetone mixtures. In media that did not contain hydrogen bond donors, the pull-off forces were found to be in very good agreement with theoretic predictions based on the Lifshitz theory. As the hydrogen bond donor ability of the medium increased, the adhesion energy was found to be increasingly underestimated by the model, illustrating the importance of the medium–medium interactions outside the contact area in determining the adhesive properties of the contact at the nanoscale. Exceptionally, in n-octanol, the pull-off forces were considerably lower than predicted and a dual slope linear friction–load relation was observed. These observations were rationalized by the formation of physisorbed layers of octanol on the surfaces. The friction–load relationship in the other media was found to be dependent on the magnitude of adhesion. For weakly adhering systems, the friction–load relationship was linear, but as adhesion increased, a sublinear relationship was observed. The data were rationalized by treating the friction as the sum of an adhesion-dependent shear term characterized by a surface shear strength τ and a molecular plowing term characterized by a coefficient of friction μ. Thus, Amontons’ law appears to describe the limiting case of very weak adhesion where viscoelastic plowing is primarily responsible for energy dissipation, while a sublinear friction–load relationship emerges in other situations due to the dissipation of energy in shearing adhesive contacts.