Correlating the Segmental Relaxation Time of Polystyrene

Polymers (Basel). 2024 Jul 29;16(15):2154. doi: 10.3390/polym16152154.

Abstract

A previous related paper dealing with the density relaxation of polystyrene (PS) has shown that the equilibrium relaxation time (τeq) has a purely exponential temperature dependence (ETD) below ≈100 °C. Such an ETD is now also confirmed based upon available dielectric spectra data for PS. By combining the ETD behavior of τeq (or aT) at low temperatures with a VFTH behavior at higher temperatures (based mainly on available recoverable shear compliance data), a composite correlation for τeq (or aT) is developed, which is continuous with continuous slope at a crossover temperature that is found to be 99.22 °C, where τeq = 92.15 s. This composite representation is shown to describe (without any adjustable parameters) available independent data for the segmental relaxation time over a finite range both above and below Tcrossover (i.e., the glass transition temperature).

Keywords: VFTH model; equilibrium relaxation time; glass transition temperature; glass–rubber transition; polystyrene; segmental relaxation time.

Grants and funding

This research received no external funding.