Influence of Cohesive Energy and Chain Stiffness on Polymer Glass Formation

TL;DR

This study uses the generalized entropy theory to explore how microscopic cohesive energy and chain stiffness influence polymer glass formation, revealing key design principles and the fundamental role of fragility.

Contribution

It introduces simple fitting formulas and identifies iso-fragility and iso-$T_g$ lines, advancing understanding of microscopic factors affecting polymer glass transition.

Findings

Rigid polymers with weak interactions are most fragile.

Stiffer chains and stronger interactions increase $T_g$.

Iso-fragility lines show invariant thermodynamic properties.

Abstract

The generalized entropy theory is applied to assess the joint influence of the microscopic cohesive energy and chain stiffness on glass formation in polymer melts using a minimal model containing a single bending energy and a single (monomer averaged) nearest neighbor van der Waals energy. The analysis focuses on the combined impact of the microscopic cohesive energy and chain stiffness on the magnitudes of the isobaric fragility parameter $m_P$ and the glass transition temperature $T_g$. The computations imply that polymers with rigid structures and weak nearest neighbor interactions are the most fragile, while $T_g$ becomes larger when the chains are stiffer and/or nearest neighbor interactions are stronger. Two simple fitting formulas summarize the computations describing the dependence of $m_P$ and $T_g$ on the microscopic cohesive and bending energies. The consideration of the combined influence of the microscopic cohesive and bending energies leads to the identification of some important design concepts, such as iso-fragility and iso-$T_g$ lines, where, for instance, iso-fragility lines are contours with constant $m_P$ but variable $T_g$. Several thermodynamic properties are found to remain invariant along the iso-fragility lines, while no special characteristics are detected along the iso-$T_g$ lines. Our analysis supports the widely held view that fragility provides more fundamental insight for the description of glass formation than $T_g$.