Modeling Sorption of Hydrocarbons in Polyethylene with the SAFT-γ Mie Approach Combined with a Statistical-Mechanical Model to Describe Semicrystalline Polymers.

A recently developed statistical-mechanical model is applied systematically to estimate the fraction of tie-molecules (polymer chains linking different crystals directly or via entanglements) in semicrystalline polyethylene (PE) samples. The amorphous domains of the polymer are divided into constrained interlamellar domains and "free" outer-lamellar domains. A set of model parameters is assigned to each sample by correlating previous experimental measurements and minimizing the difference between the predicted solubility of pure hydrocarbons in the sample and the experimental values. We show that the sorption isotherms of multiple pure fluids in each sample can be described by a single parameter set, proving that the polymer-solute interactions (described accurately by the SAFT-γ Mie EoS) are decoupled from the sample-specific properties of the polymer. We find that ∼30% of the crystalline stems in the lamellae of PE are connected to tie-molecules, within the bounds suggested by previous theoretical and computational work. The transferability of the sample-specific parameters is assessed by predicting cosolubility effects and solubility at different temperatures, leading to good agreement with experimental data.

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© 2023 The Authors. Published by American Chemical Society.

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The authors declare no competing financial interest.