Simulation studies on architecture dependence of unentangled polymer melts

The dependences of the properties of linear, ring, star, and H-shaped polymer melts on architecture are investigated by nonequilibrium molecular dynamics simulations. We find that zero-shear viscosities η₀ for various architectures follow a universal relation, $η 0 = C η 〈 R g 0 2 〉$⁠, where C_η is a constant and $〈 R g 0 2 〉$ the equilibrium mean-square radius of gyration, in the unentangled regime. This law is also found valid for asymmetrical polymers but invalid for polymers with a hard core, such as stars with many arms and short arm lengths. In the unentangled regime, from the point of view of polymer size, the relaxation times show weak dependences on architecture, but the architecture dependence of the diffusion coefficient is still apparent. Then, we examine unentangled melts of various architectures having the same size over a wide range of shear rates covering linear and nonlinear viscoelastic regimes and find that the rheological quantities, namely, viscosity, first and second normal stress differences, are independent of architecture. In contrast, the polymer deformation shows an apparent dependence on architecture in the nonlinear regime. These findings shall shed significant light on the nature of rheological behaviors of unentangled melts.