Friction of polyaromatic thiol monolayers in adhesive and nonadhesive contacts

We have used friction force microscopy to study the effects of adhesion on the boundary friction of self-assembled monolayers of the aromatic compounds thiophenol, p-phenylthiophenol, p-terphenyl thiol, 2-naphthalenethiol, and benzyl mercaptan on gold. To control the adhesion between the monolayer-covered tip and substrate, the friction measurements were made in dry N(2) gas or in ethanol. At low loads, low adhesion (in ethanol) resulted in a linear dependence of the friction force on load (i.e., F = muL) whereas higher adhesion between the same monolayers (in N(2)) gave an apparent area-dependent friction. The friction in the adhesive systems was well described by F = S(c)A with the contact area, A, calculated for a thin, linearly elastic film confined between rigid substrates using the thin-coating contact mechanics (TCCM) model in a transition regime between its DMT- and JKR-like limits. With increasing packing density of the monolayers, a systematic decrease was found in the friction coefficient (mu) obtained in ethanol and the critical shear stress (S(c)) obtained in N(2). To describe these aromatic monolayers with the extended TCCM model, a higher Young's modulus was neeeded than for fatty acid monolayers of similar packing density.