Molecular origin of shear thickening in transient polymer networks: A molecular dynamics study

Abstract

This paper proposes a simple model of transient networks of telechelic associating polymers for molecular simulations and reports the main results obtained by molecular dynamics on the rheological properties of the transient networks. The steady shear viscosity obtained by the non-equilibrium molecular dynamics simulation exhibits shear thickening at moderate shear rates and shear thinning at larger shear rates. The behavior is similar to that observed in experiments of telechelic associating polymers. By analyzing the distribution function of the end-to-end vector of bridge chains as a function of the shear rate, we find that shear thickening is mainly caused by the stress from the bridge chains highly stretched by shear flow. We also find that fracture of the transient network occurs in the shear-thinning regime at high shear rates.