Temperature- and Rate-Dependent Fracture in Disulfide Vitrimers

The fracture behaviors of disulfide vitrimers are highly rate-dependent. Our investigation revealed that the temperature-dependent fracture behaviors of disulfide vitrimers cannot be entirely explained by a simple time-temperature superposition model. This Letter explores the impact of the dynamic nature of molecular defects on the temperature- and rate-dependent fracture behaviors of disulfide vitrimers. Considering that the high cross-linking density remains constant during the associated bond exchange reaction, we identify loop defects in the network as the primary dynamic defects. By employing small amplitude oscillatory shear, we measured the loop defect fraction in EPS25 disulfide vitrimers at varied temperatures, revealing an increased presence of loop defects at elevated temperatures. Furthermore, our findings indicate that the temperature-dependent fracture behaviors are attributed to the temperature-dependent number of loop defects in disulfide vitrimers.