Adsorption-desorption kinetics in nanoscopically confined oligomer films under shear

The method of molecular dynamics computer simulations is employed to study oligomer melts confined in ultra-thin films and subjected to shear. The focus is on the self-diffusion of oligomers near attractive surfaces and on their desorption, together with the effects of increasing energy of adsorption and shear. It is found that the mobility of the oligomers near an attractive surface is strongly decreased. Moreover, although shearing the system forces the chains to stretch parallel to the surfaces and thus increase the energy of adsorption per chain, flow also promotes desorption. The study of chain desorption kinetics reveals the molecular processes responsible for the enhancement of desorption under shear. They involve sequences of conformations starting with a desorbed tail and proceeding in a very fast, correlated, segment-by-segment manner to the desorption of the oligomers from the surfaces.

Motion of a driven tracer particle in a one-dimensional symmetric lattice gas

We study the dynamics of a tracer particle subject to a constant driving force $E$ in a one-dimensional lattice gas of hard-core particles whose transition rates are symmetric. We show that the mean displacement of the driven tracer grows in time, $t$, as $\sqrt{\alpha t}$, rather than the linear time dependence found for driven diffusion in the bath of non-interacting (ghost) particles. The prefactor $\alpha$ is determined implicitly, as the solution of a transcendental equation, for an arbitrary magnitude of the driving force and an arbitrary concentration of the lattice gas particles. In limiting cases the prefactor is obtained explicitly. Analytical predictions are seen to be in a good agreement with the results of numerical simulations.Comment: 21 pages, LaTeX, 4 Postscript fugures, to be published in Phys. Rev. E, (01Sep, 1996

Evaluation of Chemical Protective Clothing by FT-IR/ATR Spectroscopy

An attenuated total reflectance permeation cell has been used to evaluate the permeation of polymer samples from chemical protective clothing (CPC), mainly gloves, by several chemical types including a solvent, a commercial pesticide mix, and a volatile solid. Good contact between sample and ATR crystal was ensured by the use of low gas pressure. The passage of the chemicals through the CPC sample could be readily followed by analysis of sets of FT-IR spectra measured during permeation experiments. Diffusion coefficients could only be estimated. The ATR method is compared with the traditional two-compartment cell used for evaluation of CPC, and its advantages and disadvantages discussed

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 approximate to 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)-10(5) 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 Angstrom, 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