Structural and dynamical properties of thermoplastic polyurethane/fullerene nanocomposites: a molecular dynamics simulations study.

Abstract

In this work, the structural and dynamical properties of thermoplastic polyurethane (TPU)/fullerene (C60) nanocomposites are investigated using atomistic molecular dynamics simulations, focusing on the glass transition, thermal expansion, polymer mobility, polymer-C60 interactions, and diffusion behavior of C60. The results show a slight increase in the glass transition temperature (Tg) with increasing C60 weight fraction (wt%), attributed to hindered polymer dynamics, and a remarkable reduction in the coefficient of thermal expansion above Tg. Results of the mean squared displacement and the time decay of bond-reorientation autocorrelation indicate that the mobility of TPU hard segments is more restricted than that of soft segments, owing to the electrostatic attractions and the π-π stacking between isocyanate groups and C60 molecules. Analysis of TPU-C60 interaction energy reveals that the electrostatic interactions are weakened with an increase in the C60 wt%, while the van der Waals contributions become more significant due to the TPU-C60 interfacial characteristics. Further analysis shows that the translational and rotational diffusion of C60 are both increasingly suppressed with the increase of C60 wt%, indicating a violation of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations, presumably due to the polymer chain-mediated hydrodynamic interactions arising from chain bridges between neighboring C60 particles. This is highlighted by a stronger decoupling of translational-rotational diffusion and a lower ratio of translational-rotational diffusion coefficient (DT/DR) with increasing C60 wt%. This work elucidates an atomistic understanding of the structure and properties of polymer/C60 nanocomposites.