A multi-fluid model for microstructure formation in polymer membranes

We develop a multi-fluid model for a ternary polymer solution using the Rayleighian formalism of Doi and Onuki, and give an efficient pseudo-spectral method for solving both the diffusion and momentum equations that result. Subsequently, we find that the numerical simulation is capable of describing systems at the micron length-scale and easily reaches millisecond time-scales. In addition, we characterize the model thermodynamics and kinetics including the (i) phase behavior, (ii) structure of the interfaces, (iii) mutual diffusion coefficients, (iv) bulk spinodal decomposition kinetics with and without hydrodynamics and (v) spinodal decomposition in the presence of an interface with a non-solvent bath. We obtain good qualitative agreement with the expected thermodynamic and kinetic behavior. We also show that a linear stability analysis of the diffusion equation quantitatively predicts the fastest growing mode obtained from simulation and gives insight into the phase separation process relevant for the evolution of microstructure in phase-separating ternary polymer solutions.