Theory of polymers in binary solvent solutions: mean-field free energy and phase behavior

Fuente: arXiv
Saved in:
Bibliographic Details
Main Authors: Marcato, Davide, Giacometti, Achille, Maritan, Amos, Rosa, Angelo
Format: Preprint
Published: 2024
Subjects:
Online Access:
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1866915249152589824
author Marcato, Davide
Giacometti, Achille
Maritan, Amos
Rosa, Angelo
author_facet Marcato, Davide
Giacometti, Achille
Maritan, Amos
Rosa, Angelo
contents We present a lattice model for polymer solutions, explicitly incorporating interactions with a bath of solvent and cosolvent molecules. By exploiting the well-known analogy between polymer systems and the $O(n)$-vector spin model in the limit $n \to 0$, we derive an exact field-theoretic expression for the partition function of the system. The latter is then evaluated at the saddle point, providing a mean-field estimate of the free energy. The resulting expression, which conforms to the Flory-Huggins type, is then used to analyze the system's stability with respect to phase separation, complemented by a numerical approach based on convex hull evaluation. We demonstrate that this simple lattice model can effectively explain the behavior of a variety of seemingly unrelated polymer systems, which have been predominantly investigated in the past only through numerical simulations. This includes both, single-chain and multi-chain, solutions. Our findings emphasize the fundamental, mutually competing, roles of solvent and cosolvent in polymer systems.
format Preprint
id arxiv_https___arxiv_org_abs_2407_01590
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Theory of polymers in binary solvent solutions: mean-field free energy and phase behavior
Marcato, Davide
Giacometti, Achille
Maritan, Amos
Rosa, Angelo
Soft Condensed Matter
We present a lattice model for polymer solutions, explicitly incorporating interactions with a bath of solvent and cosolvent molecules. By exploiting the well-known analogy between polymer systems and the $O(n)$-vector spin model in the limit $n \to 0$, we derive an exact field-theoretic expression for the partition function of the system. The latter is then evaluated at the saddle point, providing a mean-field estimate of the free energy. The resulting expression, which conforms to the Flory-Huggins type, is then used to analyze the system's stability with respect to phase separation, complemented by a numerical approach based on convex hull evaluation. We demonstrate that this simple lattice model can effectively explain the behavior of a variety of seemingly unrelated polymer systems, which have been predominantly investigated in the past only through numerical simulations. This includes both, single-chain and multi-chain, solutions. Our findings emphasize the fundamental, mutually competing, roles of solvent and cosolvent in polymer systems.
title Theory of polymers in binary solvent solutions: mean-field free energy and phase behavior
topic Soft Condensed Matter
url https://arxiv.org/abs/2407.01590