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A multiscale scheme for simulating polymer Tg

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Abstract

All-atomistic (AA) molecular dynamics (MD) is considered as one of the desirable methods for studying glass transition temperatures (Tg) of specific polymers. However, heavy computational efforts are generally required, and the simulated Tg values are not always in good agreement with the experimental data. In this work, a multiscale scheme is proposed: first, the structural and volumetric properties based multiscale modeling is employed to parameterize the coarse-grained (CG) potentials against the AA simulations of an oligomeric melt; with the CG potentials, MD simulations are then carried out on a serial of oligomer bulks and polymer systems of interests, for which the dynamical Tg values are determined. With poly(ethylene oxide) and poly(methyl methacrylate) as typical examples, the simulated dynamical Tg values of the oligomeric bulks exhibit a linear relation with the empirical values, which is used to determine the “actual Tg” for the polymer bulk. The so-obtained Tg is found to compare very well with the experimental data. Such a computational framework can be quite promising in investigating the effects of various complex factors on polymer Tg.

The actual Tg for a polymer can be reliably predicted by rescaling the simulated dynamical Tg.

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Acknowledgments

This work is financially supported by the Natural Science Foundation of Hunan Province (2017JJ2125), the Planned Science and Technology Project of Hunan Province (2016TP1028), the Innovative Research Team in Higher Educational Institute of Hunan Province, and the Talent Support Plan of Hunan University of Humanities Science & Technology (HUHST). The author is indebted to the Molecular Simulation Center of Hunan Province (situated at Hunan University), which provided the commercial software (Materials Studio-4.0) to build the initial structural models and to perform the empirical calculations, and the Laboratory for High Performance Computing (HPC) of the Key Discipline “Computer Applied Techniques” of Hunan Province (located at HUHST), which provided the generous CPU times for completing this work.

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  1. Hunan Provincial Key Laboratory of Fine Ceramics and Powder Materials, School of Materials and Environmental Engineering, Hunan University of Humanities, Science and Technology, Loudi, 417000, Hunan, China

    Chaofu Wu

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Wu, C. A multiscale scheme for simulating polymer Tg. J Mol Model 24, 335 (2018). https://doi.org/10.1007/s00894-018-3867-5

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