Dynamical self-consistent field theory captures multi-scale physics during spinodal decomposition in a symmetric binary homopolymer blend

• Published in: The Journal of chemical physics Vol. 152; no. 10; pp. 104903 - 104914
• Main Authors: Grzetic, Douglas J., Wickham, Robert A.
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 14.03.2020
• Subjects: Chain dynamics; Coarsening; Coils; Computer simulation; Domains; Dynamics; Field theory; Physics; Self consistent fields; Spinodal decomposition; Test procedures; Time dependence
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.5142179

We study the spinodal decomposition in a symmetric, binary homopolymer blend using our recently developed dynamical self-consistent field theory. By taking the extremal solution of a dynamical functional integral, the theory reduces the interacting, multi-chain dynamics to a Smoluchowski equation describing the statistical dynamics of a single, unentangled chain in a self-consistent, time-dependent, mean force-field. We numerically solve this equation by evaluating averages over a large ensemble of replica chains, each one of which obeys single-chain Langevin dynamics, subject to the mean field. Following a quench from the disordered state, an early time spinodal instability in the blend composition develops, before even one Rouse time elapses. The dominant, unstable, growing wavelength is on the order of the coil size. The blend then enters a late-time, t, scaling regime with a growing domain size that follows the expected Lifshitz–Slyozov–Wagner t1/3 power law, a characteristic of a diffusion-driven coarsening process. These results provide a satisfying test of this new method, which correctly captures both the early and late time physics in the blend. Our simulation spans five orders-of-magnitude in time as the domains coarsen to 20 times the coil size, while remaining faithful to the dynamics of the microscopic chain model.