A comparative study of oxygen diffusion in PET and PEF using molecular modelling: Computational Insights into the Mechanism for Gas Transport in Bulk Polymer Systems

Jasmine Lightfoot; Bernardo Castro Dominguez; Steve Parker; Antoine Buchard

doi:10.1021/acs.macromol.1c01316

A comparative study of oxygen diffusion in PET and PEF using molecular modelling: Computational Insights into the Mechanism for Gas Transport in Bulk Polymer Systems

Jasmine Lightfoot, Bernardo Castro Dominguez, Steve Parker, Antoine Buchard

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Abstract

Bio-derived polyethylene furanoate (PEF) has recently gained attention as a sustainable alternative to polyethylene terephthalate (PET), amidst environmental concerns over fossil fuel depletion. Herein, we outline a computational approach to investigate the tenfold difference in barrier properties between the two materials, using a statistically robust methodology to predict diffusion coefficients from molecular dynamics simulation. Oxygen diffusion was predicted to a high level of accuracy, at 3.24 × 10–8 and 2.88 × 10–9 cm2 s–1 for PET and PEF, respectively (Dexperimental = 1.16 × 10–8 and 1.04 × 10–9 cm2 s–1). Simulations quantifiably demonstrated the contributions of ring-flipping chain dynamics on oxygen diffusion, and novel Monte Carlo techniques revealed atomistic insights into the mechanism by which this occurs. Areas of accessible volume within the polymer matrix were seen to converge to facilitate lateral oxygen displacement. Infrequent convergences in PEF, due to subdued polymer chain dynamics and higher system density, accounted for the slower oxygen diffusion relative to PET.

Original language	English
Pages (from-to)	498-510
Number of pages	13
Journal	Macromolecules
Volume	55
Issue number	2
Early online date	1 Dec 2021
DOIs	https://doi.org/10.1021/acs.macromol.1c01316
Publication status	Published - 25 Jan 2022

Bibliographical note

Funding Information:
This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath and the ARCHER UK National Supercomputing Service via our membership of the UK HEC Materials Chemistry Consortium (MCC; EPSRC EP/L000202, EP/R029431, EP/T022213). The authors thank the UK EPSRC (EP/L016354/1, studentship to J.C.L., CDT in Sustainable Chemical Technologies) and the Royal Society (UF/160021 fellowship to A.B.) for research funding.

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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Cite this

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abstract = "Bio-derived polyethylene furanoate (PEF) has recently gained attention as a sustainable alternative to polyethylene terephthalate (PET), amidst environmental concerns over fossil fuel depletion. Herein, we outline a computational approach to investigate the tenfold difference in barrier properties between the two materials, using a statistically robust methodology to predict diffusion coefficients from molecular dynamics simulation. Oxygen diffusion was predicted to a high level of accuracy, at 3.24 × 10–8 and 2.88 × 10–9 cm2 s–1 for PET and PEF, respectively (Dexperimental = 1.16 × 10–8 and 1.04 × 10–9 cm2 s–1). Simulations quantifiably demonstrated the contributions of ring-flipping chain dynamics on oxygen diffusion, and novel Monte Carlo techniques revealed atomistic insights into the mechanism by which this occurs. Areas of accessible volume within the polymer matrix were seen to converge to facilitate lateral oxygen displacement. Infrequent convergences in PEF, due to subdued polymer chain dynamics and higher system density, accounted for the slower oxygen diffusion relative to PET.",

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A comparative study of oxygen diffusion in PET and PEF using molecular modelling: Computational Insights into the Mechanism for Gas Transport in Bulk Polymer Systems

Abstract

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