Mathematical modelling of thickness and temperature dependent physical aging to O2/N2 gas separation in polymeric membranes

Abstract

Polymeric membranes are glassy materials at non-equilibrium state and inherently undergo a spontaneous evolution towards equilibrium known as physical aging. Volume relaxation characteristic during the course of aging is governed by the surrounding temperature in which the polymeric material is aged. Although there are studies to understand how polymeric materials evolve over time towards equilibrium at different operating temperatures, the theories have been developed merely in response to experimental observations and phenomenological theory at bulk glassy state without the implementation of sample size effects. Limited work has been done to characterize the physical aging process to thin polymeric films using reasonable physical parameters and mathematical models with incorporation of thermodynamics and film thickness consideration. The current work applies the Tait equation of states and thickness dependent glass transition temperature, integrated within a simple linear correlation, to model the temperature and thickness dependent physical aging. The mathematical model has been validated with experimental aging data, whereby a small deviation is observed that has been explained by intuitive reasoning pertaining to the thermodynamic parameters. The mathematical model has been further employed to study the gas transport properties of O₂ and N₂, which is anticipated to be applied in oxygen enriched combustion for generation of cleaner and higher efficiency fuel in future work.