The relationship between swelling, the difference (Δδ) in theoretical Hansen solubility parameters (HSP) between the two substances, and the change of membrane mass-transfer channel has been controversial. In this work, a completely new parameter, Swell-Cavity Ratio (SCR), defined as the ratio of membrane molecular weight cut off (MWCO), was introduced to characterize the changes in mass transfer channels before and after membrane swelling. Models of the relationship between Δδ and SCR were successfully constructed for nanoporous glassy (SCR = 0.19 × Δδ0.40) and rubbery (SCR = 17.7 × Δδ-0.93) membranes, using the swelling as a bridge. Based on this contradiction in models, we speculate that SCR variation is strongly related to the separation mechanism of the membranes. The theoretical model accurately calculates the influence of the solvent on the membrane mass transfer channel, allowing for the selection of the best membrane material and pretreatment process to maximize treatment efficiency.
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