Effects of Cross-Link Density and Distribution on Static and Dynamic Properties of Chemically Cross-Linked Polymers

Abstract

Molecular dynamics simulations have been performed to study the effects of the cross-link density and distribution on the network topology, the dynamic structural properties, the tensile mechanical properties, and the viscoelastic properties of chemically cross-linked polymers. Simulation results show that the introduction of cross-links slows the chain dynamics down and thus leads to a slight increase in the glass transition temperature. Improving the cross-link dispersion state is found to be essentially equivalent to increasing the effective cross-link density, as reflected in the network topological features. The structural relaxation behavior is analyzed in terms of the incoherent intermediate dynamic structure factor, and the characteristic α-relaxation time is examined by the MCT and VFT equation. The results indicate that the time–temperature superposition principle holds on the segmental length scale but fails on the chain length scale, where it can be valid at sufficiently high temperature above...