Non-Equilibrium in Adsorbed Polymer Layers

TL;DR

This paper reviews experimental and theoretical research on non-equilibrium effects in adsorbed polymer layers, emphasizing how adsorption kinetics and layer aging influence structure and dynamics, especially under conditions where monomer-surface sticking energies are significant.

Contribution

It provides a comprehensive analysis of non-equilibrium polymer layer behavior, highlighting the differences in chain adsorption states and the distribution of bound monomers, P(f), between equilibrium and non-equilibrium conditions.

Findings

Non-equilibrium layers show a distinct P(f) distribution compared to equilibrium layers.

Adsorption kinetics significantly influence layer structure and dynamics.

Experimental P(f) measurements align with theoretical predictions for non-equilibrium layers.

Abstract

High molecular weight polymer solutions have a powerful tendency to deposit adsorbed layers when exposed to even mildly attractive surfaces. The equilibrium properties of these dense interfacial layers have been extensively studied theoretically. A large body of experimental evidence, however, indicates that non-equilibrium effects are dominant whenever monomer-surface sticking energies are somewhat larger than kT, a common case. Polymer relaxation kinetics within the layer are then severely retarded, leading to non-equilibrium layers whose structure and dynamics depend on adsorption kinetics and layer ageing. Here we review experimental and theoretical work exploring these non-equilibrium effects, with emphasis on recent developments. The discussion addresses the structure and dynamics in non-equilibrium polymer layers adsorbed from dilute polymer solutions and from polymer melts and more concentrated solutions. Two distinct classes of behaviour arise, depending on whether physisorption or chemisorption is involved. A given adsorbed chain belonging to the layer has a certain fraction of its monomers bound to the surface, f, and the remainder belonging to loops making bulk excursions. A natural classification scheme for layers adsorbed from solution is the distribution of single chain f values, P(f), which may hold the key to quantifying the degree of irreversibility in adsorbed polymer layers. Here we calculate P(f) for equilibrium layers; we find its form is very different to the theoretical P(f) for non-equilibrium layers which are predicted to have infinitely many statistical classes of chain. Experimental measurements of P(f) are compared to these theoretical predictions.