Theory of expansion and compression of polymeric materials

TL;DR

This paper extends classical polymer swelling theories to account for directional expansion, pressure effects, and dynamic behavior, providing a comprehensive model for porous polymeric materials under various conditions.

Contribution

It introduces a modified equilibrium theory for unidirectional expansion and pressure-driven compaction, including dynamic modeling of size changes over time.

Findings

The theory predicts increased compaction with higher applied pressure.

Results show significant thickness-dependent variation in membrane porosity.

Models demonstrate dynamic size change after solvent interaction shifts.

Abstract

We extend classical Flory-Rehner theory for the expansion and compression of porous materials such as cross-linked polymer networks. The theory includes volume exclusion, affinity with the solvent, and finite stretching of the polymer chains. We also modify this equilibrium theory -- that applies to equal expansion of a material in all directions -- to the situation that a material can only expand in a single direction, as is the case when a thin layer is tightly bound to a support structure. We extend this equilibrium model to the case that a pressure is applied across such a thin layer of the polymer material, for instance a membrane, and liquid flows across this layer. The theory describes how in the direction of liquid flow the membrane is increasingly compacted (becomes less porous), and the more so at higher applied pressures. We provide results of example calculations for a thick membrane with significant changes in compaction across its thickness, and a thin membrane for which compaction due to flow is minor. In the last section we model the dynamics of the change of size of a porous material in time after a step change in the solvent-polymer attraction parameter.