Phase separation kinetics in compressible polymer solutions: Computer simulation of the early stages

TL;DR

This paper introduces a coarse-grained simulation model for polymer solutions in supercritical fluids, capturing phase separation, interface behavior, and early nucleation stages with good experimental agreement.

Contribution

The study develops a novel coarse-grained model that accurately simulates phase separation and nucleation in polymer-supercritical fluid systems, including interface and early-stage dynamics.

Findings

Model fits critical point properties of systems

Demonstrates interfacial adsorption phenomena

Visualizes early nucleation stages and deviations from classical theory

Abstract

A coarse-grained model for solutions of polymers in supercritical fluids is introduced and applied to the system of hexadecane and carbon dioxide as a representative example. Fitting parameters of the model to the gas-liquid critical point properties of the pure systems, and allowing for a suitably chosen parameter that describes the deviation from the Lorentz-Berthelot mixing rule, we model the liquid-gas and fluid-fluid unmixing transitions of this system over a wide range of temperatures and pressures in reasonable agreement with experiment. Interfaces between the polymer-rich phase and the gas can be studied both at temperatures above and below the end point of the triple line where liquid and vapor carbon dioxide and the polymer rich phase coexist. In the first case interfacial adsorption of fluid carbon dioxide can be demonstrated. Our model can also be used to simulate quenches from the one-phase to the two-phase region. A short animation and a series of snapshots help to visualize the early stages of bubble nucleation and spinodal decomposition. Furthermore we discuss deviations from classical nucleation theory for small nuclei.