Molecular friction dissipation and mode coupling in organic monolayers and polymer films.

The impact of thermally active molecular rotational and translational relaxation modes on the friction dissipation process involving smooth nano-asperity contacts has been studied by atomic force microscopy, using the widely known Eyring analysis and a recently introduced method, dubbed intrinsic friction analysis. Two distinctly different model systems, i.e., monolayers of octadecyl-phosphonic acid (ODPA) and thin films of poly(tert-butyl acrylate) (PtBA) were investigated regarding shear-rate critical dissipation phenomena originating from diverging mode coupling behaviors between the external shear perturbation and the internal molecular modes of relaxation. Rapidly (ODPA) versus slowly (PtBA) relaxing systems, in comparison to the sliding rate, revealed monotonous logarithmic and nonmonotonous spectral shear rate dependences, respectively. Shear coupled, enthalpic activation energies of 46 kJ∕mol for ODPA and of 35 and ∼65 kJ∕mol for PtBA (below and above the glass transition) were found that could be attributed to intrinsic modes of relaxations. Also, entropic energies involved in the cooperative backbone mobility of PtBA could be quantified, dwarfing the activation energy by more than a factor of five. This study provides (i) a material specific understanding of the molecular scale dissipation process in shear compliant substances, (ii) analyses of material intrinsic shear-rate mode coupling, shear coordination and energetics, (iii) a verification of Eyring's model applied to tribological systems toward material intrinsic specificity, and (iv) a valuable extension of the Eyring analysis for complex macromolecular systems that are slowly relaxing, and thus, exhibit shear-rate mode coupling.