Unexpected Ductility in Semiflexible Polymer Glasses with Entanglement Length Equal to Their Kuhn Length

Abstract

Semiflexible polymer glasses (SPGs), including those formed by the recently synthesized semiflexible conjugated polymers, are expected to be brittle because classical formulas for their craze extension ratio λ_{craze} and fracture stretch λ_{frac} predict that systems with N_{e}=C_{∞} have λ_{craze}=λ_{frac}=1 and hence cannot be deformed to large strains. Using molecular dynamics simulations, we show that in fact such glasses can form stable crazes with λ_{craze}≃N_{e}^{1/4}≃C_{∞}^{1/4}, and that they fracture at λ_{frac}=(3N_{e}^{1/2}-2)^{1/2}≃(3C_{∞}^{1/2}-2)^{1/2}. We argue that the classical formulas for λ_{craze} and λ_{frac} fail to describe SPGs' mechanical response because they do not account for Kuhn segments' ability to stretch during deformation.