Dependence of the friction process on the molecular structure and architecture of thin polymer films

The frictional properties of a homologous series of poly(n-alkyl methacrylates) (PnAMA) and a series of poly(methyl methacrylate) (PMMA) films, cast from a variety of solvents, are characterized. The choice of polymer film was driven by the consideration of the possible mechanisms for the accommodation of a macroscopically applied shear stress by molecular entities. Two possible mechanisms are proposed: (i) the relative flexibility of the polymer backbone chain. For this purpose the PnAMAs have been chosen. By varying the length of the substituent chain, the relative molecular freedom around the backbone chain is altered. These molecular differences are sensed in the frictional properties at the macroscopic level, and (ii) the molecular organization is also proposed to be a factor in determining the friction response of a particular polymer film. For this purpose, the frictional properties of PMMA films cast from different solvents are investigated. There is observed to be a strong influence of the molecular organization on the frictional properties of the solvent cast PMMA films. The molecular probe employed to characterize the molecular environment is vibrational spectroscopy. Conformationally sensitive vibrational modes are used to determine the relative flexibility of the backbone chain and the organization of the chain network.