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Dudowicz J, Freed KF, Douglas JF. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions. J Chem Phys. 2015;143(19):194901doi: 10.1063/1.4935705.
Dudowicz, J., Freed, K. F., & Douglas, J. F. (2015). Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions. The Journal of chemical physics, 143(19), 194901. https://doi.org/10.1063/1.4935705
Dudowicz, Jacek, et al. "Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions." The Journal of chemical physics vol. 143,19 (2015): 194901. doi: https://doi.org/10.1063/1.4935705
Dudowicz J, Freed KF, Douglas JF. Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions. J Chem Phys. 2015 Nov 21;143(19):194901. doi: 10.1063/1.4935705. PMID: 26590552.
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J Chem Phys. 2015 Nov 21;143(19):194901. doi: 10.1063/1.4935705.

Phase behavior and second osmotic virial coefficient for competitive polymer solvation in mixed solvent solutions.

The Journal of chemical physics

Jacek Dudowicz, Karl F Freed, Jack F Douglas

Affiliations

  1. The James Franck Institute and the Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.
  2. Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.

PMID: 26590552 DOI: 10.1063/1.4935705

Abstract

We apply our recently developed generalized Flory-Huggins (FH) type theory for the competitive solvation of polymers by two mixed solvents to explain general trends in the variation of phase boundaries and solvent quality (quantified by the second osmotic virial coefficient B2) with solvent composition. The complexity of the theoretically predicted miscibility patterns for these ternary mixtures arises from the competitive association between the polymer and the solvents and from the interplay of these associative interactions with the weak van der Waals interactions between all components of the mixture. The main focus here lies in determining the influence of the free energy parameters for polymer-solvent association (solvation) and the effective FH interaction parameters {χαβ} (driving phase separation) on the phase boundaries (specifically the spinodals), the second osmotic virial coefficient B2, and the relation between the positions of the spinodal curves and the theta temperatures at which B2 vanishes. Our classification of the predicted miscibility patterns is relevant to numerous applications of ternary polymer solutions in industrial formulations and the use of mixed solvent systems for polymer characterization, such as chromatographic separation where mixed solvents are commonly employed. A favorable comparison of B2 with experimental data for poly(methyl methacrylate)/acetonitrile/methanol (or 1-propanol) solutions only partially supports the validity of our theoretical predictions due to the lack of enough experimental data and the neglect of the self and mutual association of the solvents.

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