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Bibliographic Details
Main Authors: McDonald, Jared, von Spakovsky, Michael R., Reynolds Jr, William T.
Format: Preprint
Published: 2023
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Online Access:https://arxiv.org/abs/2304.04105
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author McDonald, Jared
von Spakovsky, Michael R.
Reynolds Jr, William T.
author_facet McDonald, Jared
von Spakovsky, Michael R.
Reynolds Jr, William T.
contents 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 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 experimental density profiles. The Flory-Huggins parameter chosen to describe brush-solvent interactions affects the solvent distribution in the brush but has minimal impact on the polymer density profile. Three types of non-equilibrium 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.
format Preprint
id arxiv_https___arxiv_org_abs_2304_04105
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Predicting Polymer Brush Behavior in Solvents using the Steepest-Entropy-Ascent Quantum Thermodynamic Framework
McDonald, Jared
von Spakovsky, Michael R.
Reynolds Jr, William T.
Soft Condensed Matter
Materials Science
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 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 experimental density profiles. The Flory-Huggins parameter chosen to describe brush-solvent interactions affects the solvent distribution in the brush but has minimal impact on the polymer density profile. Three types of non-equilibrium 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.
title Predicting Polymer Brush Behavior in Solvents using the Steepest-Entropy-Ascent Quantum Thermodynamic Framework
topic Soft Condensed Matter
Materials Science
url https://arxiv.org/abs/2304.04105