Associative and Segregative Liquid-Liquid Phase Separation in Macromolecular Solutions

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Autores principales: Tuinier, Remco, Garcia, Alvaro Gonzalez
Formato: Preprint
Publicado: 2025
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author Tuinier, Remco
Garcia, Alvaro Gonzalez
author_facet Tuinier, Remco
Garcia, Alvaro Gonzalez
contents We investigate liquid-liquid phase separation (LLPS) and interfacial properties of two LLPS modes: associative (ALLPS) and segregative (SLLPS). Analytical expressions for the critical point (CP) and binodal boundaries are derived and show excellent agreement with self-consistent field (SCF) lattice computations. Distinct thermodynamic features differentiate ALLPS from SLLPS: (1) in ALLPS, polymers co-concentrate within a single dense phase coexisting with a solvent-rich phase, whereas in SLLPS each polymer forms a separate phase; (2) the attractive interaction per monomer in ALLPS is strongly dependent on solvent quality, but solvent-independent in SLLPS; and (3) ALLPS binodals exhibit near-universal behavior, largely independent of solvent content. SCF results further show that interfacial tension increases and interfacial width decreases with distance from the CP. We provide scaling relations for both quantities are provided. Compared with SLLPS, ALLPS displays higher interfacial tension and a thinner interface, reflecting distinct molecular organization at the liquid-liquid boundary.
format Preprint
id arxiv_https___arxiv_org_abs_2510_25493
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Associative and Segregative Liquid-Liquid Phase Separation in Macromolecular Solutions
Tuinier, Remco
Garcia, Alvaro Gonzalez
Soft Condensed Matter
Chemical Physics
We investigate liquid-liquid phase separation (LLPS) and interfacial properties of two LLPS modes: associative (ALLPS) and segregative (SLLPS). Analytical expressions for the critical point (CP) and binodal boundaries are derived and show excellent agreement with self-consistent field (SCF) lattice computations. Distinct thermodynamic features differentiate ALLPS from SLLPS: (1) in ALLPS, polymers co-concentrate within a single dense phase coexisting with a solvent-rich phase, whereas in SLLPS each polymer forms a separate phase; (2) the attractive interaction per monomer in ALLPS is strongly dependent on solvent quality, but solvent-independent in SLLPS; and (3) ALLPS binodals exhibit near-universal behavior, largely independent of solvent content. SCF results further show that interfacial tension increases and interfacial width decreases with distance from the CP. We provide scaling relations for both quantities are provided. Compared with SLLPS, ALLPS displays higher interfacial tension and a thinner interface, reflecting distinct molecular organization at the liquid-liquid boundary.
title Associative and Segregative Liquid-Liquid Phase Separation in Macromolecular Solutions
topic Soft Condensed Matter
Chemical Physics
url https://arxiv.org/abs/2510.25493