Macromolecules, Vol.52, No.20, 7704-7720, 2019
Collective Short-Time Dynamics in Multicomponent Polymer Melts
On short length and time scales, the collective kinetics of relaxation or structure formation in multicomponent polymer melts, such as homopolymer blends and copolymers, is influenced by the subdiffusive single-chain dynamics. We compare the predictions of the dynamic random-phase approximation (D-RPA) and dynamic self-consistent field theory (D-SCFT) to that of particle-based simulation, focusing on the decay of a density fluctuation in the disordered phase, the spinodal phase separation after a quench from the disordered phase, and the response of the disordered phase to an external field. D-SCFT with a wavevector-dependent Onsager coefficient qualitatively fails to predict the time evolution on time scales shorter than the Rouse relaxation time of the underlying polymers, whereas D-RPA successfully captures the collective behavior observed in particle-based simulation. Extensions of D-SCFT, employing a time-dependent Onsager coefficient that is derived from D-RPA and that accounts for the subdiffusive single-chain dynamics on short time scales, are discussed.