Mesoscopic theory of the viscoelasticity of polymers

We have advanced our previous static theory of polymer entanglement involving an extended Cahn-Hilliard functional, to include time-dependent dynamics. We go beyond the Gaussian approximation, to the one-loop level, to compute the frequency dependent storage and loss moduli of the system. The three parameters in our theory are obtained by fitting to available experimental data on polystyrene melts of various chain lengths. This provides a physical representation of the parameters in terms of the chain length of the system. We discuss the importance of the various terms in our energy functional with respect to their contribution to the viscoelastic response of the polymeric system.Comment: Submitted to Phys. Rev.

Onset of entanglement

We have developed a theory of polymer entanglement using an extended Cahn-Hilliard functional, with two extra terms. One is a nonlocal attractive term, operating over mesoscales, which is interpreted as giving rise to entanglement, and the other a local repulsive term indicative of excluded volume interactions. We show how such a functional can be derived using notions from gauge theory. We go beyond the Gaussian approximation, to the one-loop level, to show that the system exhibits a crossover to a state of entanglement as the average chain length between points of entanglement decreases. This crossover is marked by critical slowing down, as the effective diffusion constant goes to zero. We have also computed the tensile modulus of the system, and we find a corresponding crossover to a regime of high modulus.Comment: 18 pages, with 4 figure