Macromolecules, Vol.30, No.15, 4459-4463, 1997
Viscoelastic Effects on the Early Stages of Phase-Separation in Polymer Blends
We modify the Cahn-Hilliard theory of concentration fluctuation dynamics to account for the short-time networklike nature of high molecular weight polymers. We propose an additional term in the free energy, due to elastic energy arising from the finite lifetime of entanglements. If we assume a single-exponential decay time for the entanglements, the equation of motion is governed by two exponential modes. For quenches into the two-phase region, the faster mode always decays with time, and the slower mode grows. The theory successfully accounts for data from spinodal decomposition of polymer blends containing at least one component of very high molecular weight.