Generalized entropy theory of glass-formation in fully flexible polymer melts

TL;DR

This paper extends the generalized entropy theory to fully flexible polymer melts, revealing universal scaling laws and thermodynamic behaviors consistent with simulations, and predicts residual configurational entropy at low temperatures.

Contribution

It introduces a GET framework for fully flexible polymers, previously limited to semiflexible chains, and uncovers universal scaling and residual entropy predictions.

Findings

Thermodynamic properties scale with temperature divided by cohesive energy $\\epsilon$.

Characteristic glass transition temperatures increase linearly with $\\epsilon$.

Residual configurational entropy persists at low temperatures, indicating Arrhenius relaxation.

Abstract

The generalized entropy theory (GET) offers many insights into how molecular parameters influence polymer glass-formation. Given the fact that chain rigidity often plays a critical role in understanding the glass-formation of polymer materials, the GET was originally developed based on models of semiflexible chains. Consequently, all previous calculations within the GET considered polymers with some degree of chain rigidity. Motivated by unexpected results from computer simulations of fully flexible polymer melts concerning the dependence of thermodynamic and dynamic properties on the cohesive interaction strength ($\epsilon$), the present paper employs the GET to explore the influence of $\epsilon$ on glass-formation in models of polymer melts with a vanishing bending rigidity, i.e., fully flexible polymer melts. In accord with simulations, the GET for fully flexible polymer melts predicts that basic dimensionless thermodynamic properties (such as the thermal expansion coefficient and isothermal compressibility) are universal functions of the temperature scaled by $\epsilon$ in the regime of low pressures. Similar scaling behavior is also found for the configurational entropy density in the GET for fully flexible polymer melts. Moreover, we find that the characteristic temperatures of glass-formation increase linearly with $\epsilon$ and that the fragility is independent of $\epsilon$ in fully flexible polymer melts, predictions that are again consistent with simulations of glass-forming polymer melts composed of fully flexible chains. Beyond an explanation of these general trends observed in simulations, the GET for fully flexible polymer melts predicts the presence of a positive residual configurational entropy at low temperatures, indicating a return to Arrhenius relaxation in the low temperature glassy state.