Bulk and interfacial shear thinning of immiscible polymers

Nonequilibrium molecular-dynamics simulations are used to study the shear-thinning behavior of immiscible symmetric polymer blends. The phase-separated polymers are subjected to a simple shear flow imposed by moving a wall parallel to the fluid-fluid interface. The viscosity begins to shear thin at much lower rates in the bulk than at the interface. The entire shear-rate dependence of the interfacial viscosity is consistent with a shorter effective chain length s(*) that also describes the width of the interface. This s(*) is independent of chain length N and is a function only of the degree of immiscibility of the two polymers. Changes in polymer conformation are studied as a function of position and shear rate. Shear thinning correlates more closely with a decrease in the component of the radius of gyration along the velocity gradient than with elongation along the flow. At the interface, this contraction of chains is independent of N and consistent with the bulk behavior for chains of length s(*). The distribution of conformational changes along chains is also studied. Central regions begin to stretch at a shear rate that decreases with increasing N, while shear induced changes at the ends of chains are independent of N.