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Amorphous cis-1,4-polybutadiene P–V-T properties from atomistic simulations

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Abstract

Context

As a result of the diversity of microstructures encountered in cis-1,4-polybutadiene and the variety of measurement methods used, experimental values of variation of glass transition temperature (Tg) with pressure are relatively dispersed. However, atomistic simulations enable access to valuable information for very well-controlled chemistry and structures with a well-defined and systematic acquisition protocol. By varying the temperature and pressure, the specific volume of the melt was computed, yielding results that deviated by only 2% from experimental data. A linear relationship between Tg and pressure was observed, with Tg predicted to be 162 K at zero pressure and a rate of change of Tg with respect to pressure (dTg/dP) of 0.24 K/MPa.

Method

The atomistic dilatometry experiments were conducted on a model of amorphous cis-1,4 polybutadiene with an approximate molecular weight of 5400 g/mol using the LAMMPS code and the all-atom forcefield pcff + . The dilatometry process involved cooling and heating at a rate of 9 × 1012 K/min. The specific volume was calculated by averaging over seven independent configurations for each temperature. The Tait equation was employed to fit the specific volume evolution within the temperature range of 10 to 700 K under different pressures of 0, 60, and 100 MPa.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

A.Shamsieva and I.Piyanzina’s work is supported by the Kazan Federal University Strategic Academic Leadership Program (PRIORITY-2030).

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Authors and Affiliations

  1. Institute of Physics, Kazan Federal University, Kremlyovskaya St. 18, Kazan, 420008, Republic of Tatarstan, Russia

    Aigul Shamsieva & Irina Piyanzina

  2. Materials Design SARL, 42 Avenue Verdier, 92120, Paris, Montrouge, France

    Benoit Minisini

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  1. Aigul Shamsieva
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  2. Irina Piyanzina
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All authors contributed to the study conception and design. Methodology was proposed by B. Minisini and applied by A. Shamseiva and I. Piyanzina. The first draft of the manuscript was written by B. Minisini, and all authors commented and improved on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Benoit Minisini.

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Shamsieva, A., Piyanzina, I. & Minisini, B. Amorphous cis-1,4-polybutadiene P–V-T properties from atomistic simulations. J Mol Model 29, 249 (2023). https://doi.org/10.1007/s00894-023-05658-6

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