Structure and dynamical intra-molecular heterogeneity of star polymer melts above glass transition temperature

A Chremos and E Glynos and PF Green, JOURNAL OF CHEMICAL PHYSICS, 142, 044901 (2015).

DOI: 10.1063/1.4906085

Structural and dynamical properties of star melts have been investigated with molecular dynamics simulations of a bead-spring model. Star polymers are known to be heterogeneous, but a systematic simulation study of their properties in melt conditions near the glass transition temperature was lacking. To probe their properties, we have expanded from linear to star polymers the applicability of Dobkowski's chain- length dependence correlation function Z. Dobkowski, Eur. Polym. J. 18, 563 (1982). The density and the isokinetic temperature, based on the canonical definition of the laboratory glass-transition, can be described well by the correlation function and a subtle behavior manifests as the architecture becomes more complex. For linear polymer chains and low functionality star polymers, we find that an increase of the arm length would result in an increase of the density and the isokinetic temperature, but high functionality star polymers have the opposite behavior. The effect between low and high functionalities is more pronounced for short arm lengths. Complementary results such as the specific volume and number of neighbors in contact provide further insights on the subtle relation between structure and dynamics. The findings would be valuable to polymer, colloidal, and nanocomposites fields for the design of materials in absence of solution with the desired properties. (C) 2015 AIP Publishing LLC.

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