Brownian simulations of a network of reptating primitive chains

Abstract

A new model for Brownian dynamics simulations of entangled polymeric liquids is proposed here. Chains are coarse grained at the level of segments between consecutive entanglements; hence, the system is in fact a network of primitive chains. The model incorporates not only the “individual” mechanisms of reptation and tube length fluctuation, but also collective contributions arising from the 3D network structure of the entangled system, such as constraint release. Chain coupling is achieved by fulfilling force balance on the entanglement nodes. The Langevin equation for the nodes contains both the tension in the chain segments emanating from the node and an osmotic force arising from density fluctuations. Entanglements are modeled as slip links, each connecting two chain strands. The motion of monomers through slip links, which ultimately generates reptation as well as tube length fluctuations, is also described by a suitable Langevin equation. Creation and release of entanglements is controlled by the number of monomers at the chain ends. In a creation event, the partner chain segment is chosen randomly among those spatially close to the advancing chain end. To validate the model, equilibrium dynamics simulations were run for monodisperse linear chains containing up to Z=40 entanglements. The results show, in agreement with experiments, (i) a Z3.5±0.1 dependence of the longest relaxation time, (ii) a Z−2.4±0.2 dependence of the self-diffusion coefficient, and (iii) a relaxation modulus proportional to the square of the end-to-end vector correlation function, consistently with the dynamic tube dilation concept.