A blob model to parameterize polymer hole free volumes and solute diffusion

作者：Yan Zhu, Frank Welle, Olivier Vitrac · 发表于：Soft Matter · 年份：2019 · DOI：10.1039/c9sm01556f · 被引用次数：12 · 研究领域：Rheology and Fluid Dynamics Studies、Material Properties and Processing、Advanced Cellulose Research Studies

≤ 160 K). The new parameterization of the concept of hole-free volumes opens the application of the free-volume theory (FVT) developed by Vrentas and Duda to practically any polymer, regardless of the availability of free-volume parameters. The quality of the estimations was tested with various probes including n-alkanes, 1-alcohols, n-alkyl acetates, and n-alkylbenzene. The effects of enthalpic and entropic effects of the blobs and the anchor were analyzed and quantified. Blind validation of the reformulated FVT was tested successfully by predicting from first principles the diffusivities of water and toluene in amorphous polyethylene terephthalate from 4 °C to 180 °C and in various other polymers. The new blob model would open the rational design of additives with controlled diffusivities in thermoplastics.