Contact Mechanics of Nanometer-Scale Molecular Contacts: Correlation between Adhesion, Friction, and Hydrogen Bond Thermodynamics

Using a scanning force microscope, adhesion forces have been measured between carboxylic acid terminated self-assembled monolayers in different nonpolar solvents or in two-component liquid mixtures consisting of a polar solvent (ethyl acetate or acetone) in heptane. The adhesion forces measured in pure acetone and ethyl acetate were small (0.24 nN) but increased logarithmically as the concentration of the polar solvent decreased to reach a maximum value (2.77 nN), equal to that measured in pure heptane, and for lower concentrations of polar solvent, the adhesion force remained constant. This behavior is identical to that observed for association constants measured for the formation of 1:1 H-bonded complexes between dilute solutes in solvent mixtures. The transition between the solvent-dependent and -independent regimes occurs at a polar solvent concentration corresponding to 1/K_S, where K_S is the equilibrium constant for solvation of a carboxylic acid by the polar solvent in heptane. A simple model, in which the solvation of the carboxylic acid groups may be estimated by considering the concentration and polarity of functional groups in the liquid, accurately predicts values of K_S that were found to correlate very well with the observed solvent-dependence of the adhesion force. Friction–load relationships were measured using friction-force microscopy. In pure acetone and ethyl acetate, a linear friction–load relationship was observed, in agreement with Amontons’ law. However, as the concentration of polar solvent was reduced, a nonlinear relationship was observed and the friction–load relationship was found to fit the Derjaguin–Müller–Toporov (DMT) model for single asperity contacts. For pure heptane and a range of other nonpolar liquids with identical dielectric constants, the friction–load relationship was described by DMT mechanics. Exceptionally, for perfluorodecalin, Johnson–Kendall–Roberts mechanics was observed. These observations may be rationalized by treating the friction force as the sum of load-dependent and shear contributions. Under conditions of low adhesion, where the carboxylic acid surface is solvated by polar solvent molecules, the shear term is negligible and the sliding interaction is dominated by load-dependent friction. As the degree of solvation of the carboxylic acid groups decreases and the adhesion force increases, the shear friction contribution increases, dominating the interaction for media in which the adhesion force is greater than ca. 0.6 nN.