Description of Gas Transport in Polymers: Integrated Thermodynamic and Transport Modeling of Refrigerant Gases in Polymeric Membranes.

Hydrofluorocarbons (HFC) are today widely used as refrigerants, solvents, or aerosols for fire protection. Due to their non-negligible environmental impact, there exists an increasing interest towards their effective separation and recovery, which still remains a major challenge. This work presents a comprehensive thermodynamic and transport modeling approach able to describe HFC sorption and transport in different amorphous polymers, including glassy, rubbery, and copolymers, as well as in supported Ionic Liquid membranes (SILMs). In particular, the literature solubility data for refrigerants such as R-32, R-125, R-134a, and R-152a is analyzed by means of the Sanchez-Lacombe Equation of State (SL-EoS), and its non-equilibrium extension (NELF), to predict gas uptake in complex polymeric materials. The Standard Transport Model (STM) is then employed to describe permeability behaviors, incorporating concentration-dependent diffusion using a mobility coefficient and thermodynamic factor. Results demonstrate that fluorinated gases exhibit strong affinity to fluorinated and high free-volume polymers, and that solubility is primarily governed by gas condensability, molecular size, and polymer structure. The combined EoS-STM approach accurately predicts both solubility and permeability across different pressures in all polymers, including SILM. The thorough study of HFC transport in polymer membranes provided both systematic insights and predictive capabilities to guide the design of next-generation materials for refrigerant recovery and low-GWP separation processes.