Effect of functionality on unentangled star polymers at equilibrium and under shear flow.

The properties of unentangled star polymers with arm length Nf = 20 beads and functionality f (3 ≤ f ≤ 60) are investigated at equilibrium and under shear flow by coarse-grained molecular dynamics simulations. At equilibrium, the star polymer shows a crossover from a linear, freely penetrable, extremely soft object to a spherical, slightly hard object with an impenetrable center with increasing f. The results confirm that the arm relaxation is essentially independent of f and stars of large f form a liquid-like structure. In shear flow, the polymer deformation and alignment are calculated as well as the shear-induced rotational dynamics as function of shear rate. These properties are found to exhibit qualitative changes at an f-independent shear rate, γṗ, which is a consequence of competition between chain relaxation and imposed flow. Shear thinning is characterized by shear viscosity and normal stress differences. With increasing f, the critical shear rate for the onset of shear thinning decreases from γṗ for f = 3 to a smaller value. Our results also show that shear thinning of stars of large f arise from the collapse of liquid-like structures at low shear rates (γ̇≪γṗ), where chains have no deformation; at high shear rates (γ̇≫γṗ), shear thinning is mainly attributed to the chain stretching and orientation as linear polymers.