Tribology of Confined Fomblin-Z Perfluoropolyalkyl Ethers: Role of Chain-End Chemical Functionality

Strong dependence of the tribological response upon the nature of the polar end groups of perfluorinated linear chains was observed for Fomblin-Z perfluoropolyalkyl ethers of similar length and composition but terminated by a different polar group at both chain ends. The number-average molecular weight of the polymers was M_n ≈ 2000 g mol^-1 and the chain-end functionality was either carboxylic acid, hydroxyl, piperonyl, or the p-phenoxyanilinium salt of a carboxylic acid. The method of investigation was a surface forces apparatus modified for dynamic oscillatory shear at variable frequency and effective shear rate. Differences were observed as concerns not only the shear forces but also the minimum thickness to which the films could be compressed under a given normal load and the adhesion measured on separation of the surfaces after prior compression. The shear forces were studied at normal pressures of 1 and 3 MPa, both in the linear viscoelastic regime and at high shear amplitudes corresponding to shear rates of 10^-2-10⁵ s^-1. The carboxylic acid terminated polymer displayed solidlike responses to shear, possibly reflecting dimerization owing to hydrogen bonding. This contrasted with the more fluidlike shear rheology of the hydroxyl- and piperonyl-terminated polymers, in which the association from hydrogen bonding and polar interactions is believed to be weaker and result in a different structure. The sample comprised of the p-phenoxyanilinium salt of a carboxylic acid could not be compressed to less than an exceptionally large film thickness, around 100 Å, and did not appear to solidify at the pressures studied. This study suggests that not only the affinity of the functionalized chain ends to a solid surface but also the self-association of polar end groups in the nonpolar environment of fluorinated chains influences the lubricating performance of these films.