Simulations of tensile failure in glassy polymers: effect of cross-link density

Abstract

Molecular dynamics simulations are adopted to investigate the failure mechanisms of glassy polymers, particularly with respect to increasing density of cross-links. In our simulations thermosetting polymers, which are cross-linked, exhibit an embrittlement compared with uncross-linked thermoplastics in a similar fashion to several experimental investigations (Levita et al 1991 J. Mater. Sci. 26 2348; Sambasivam et al 1997 J. Appl. Polym. Sci. 65 1001; Iijima et al 1992 Eur. Polym. J. 28 573). We perform a detailed analysis of this phenomenon and propose an interpretation based on the predominance of chain scission process over disentanglement in thermosetting polymers. We also elucidate the brittle fracture response of the thermosetting polymers.