Predicting Polymer Brush Behavior in Solvents Using the Steepest-Entropy-Ascent Quantum Thermodynamic Framework.

Abstract

The steepest-entropy-ascent quantum thermodynamic (SEAQT) framework is utilized to study the effects of temperature on polymer brushes. The brushes are represented by a discrete energy spectrum, and energy degeneracies obtained through the replica-exchange Wang-Landau algorithm. The SEAQT equation of motion is applied to the density of states to establish a unique kinetic path from an initial thermodynamic state to a stable equilibrium state. The kinetic path describes the brush's evolution in state space, as it interacts with a thermal reservoir. The predicted occupation probabilities along the kinetic path are used to determine the expected thermodynamic and structural properties. The polymer density profile of a polystyrene brush in cyclohexane solvent is predicted using the equation of motion, and it agrees qualitatively with the experimental density profiles. The Flory-Huggins parameter chosen to describe brush-solvent interactions affects the solvent distribution in the brush but has a minimal impact on the polymer density profile. Three types of nonequilibrium kinetic paths with differing amounts of entropy production are considered: a heating path, a cooling path, and a heating-cooling path. Properties such as tortuosity, radius of gyration, brush density, solvent density, and brush chain conformations are calculated for each path.