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

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.

arXiv comment10 pages, 8 figures, to be published in the Journal of Chemical Physics

References in corpus (7)

• The Relationship of Dynamical Heterogeneity to the Adam-Gibbs and Random First-Order Transition Theories of Glass Formation
• Influence of Cohesive Energy and Chain Stiffness on Polymer Glass Formation
• Lattice cluster theory for polymer melts with specific interactions
• Generalized Entropy Theory of Glass Formation in Polymer Melts with Specific Interactions
• Qualitative change in structural dynamics of some glass-forming systems
• Polymer Glass-Formation in Variable Dimension
• Thermodynamic scaling of dynamics in polymer melts: Predictions from the generalized entropy theory

Cited by in corpus (5)

• Perspective: Configurational entropy of glass-forming liquids
• Zero-temperature glass transition in two dimensions
• Polymer Glass Formation: Role of Activation Free Energy, Configurational Entropy, and Collective Motion
• Systematic Coarse-graining of Epoxy Resins with Machine Learning-Informed Energy Renormalization
• Crystal melting influenced by particle cooperativity of the liquid