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Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures

V. F. D. Peters, M. Vis, Á. González García, H. H. Wensink, and R. Tuinier
Phys. Rev. Lett. 125, 127803 – Published 18 September 2020
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Abstract

Using a minimal algebraic model for the thermodynamics of binary rod-polymer mixtures, we provide evidence for a quintuple phase equilibrium; an observation that seems to be at odds with the Gibbs phase rule for two-component systems. Our model is based on equations of state for the relevant liquid crystal phases that are in quantitative agreement with computer simulations. We argue that the appearance of a quintuple equilibrium, involving an isotropic fluid, a nematic and smectic liquid crystal, and two solid phases, can be reconciled with a generalized Gibbs phase rule in which the two intrinsic length scales of the athermal colloid-polymer mixture act as additional field variables.

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  • Received 27 March 2020
  • Accepted 10 July 2020

DOI:https://doi.org/10.1103/PhysRevLett.125.127803

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.

Published by the American Physical Society

Physics Subject Headings (PhySH)

Polymers & Soft Matter

Authors & Affiliations

V. F. D. Peters1, M. Vis1,2, Á. González García1,3, H. H. Wensink4, and R. Tuinier1,3,*

  • 1Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry & Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, Netherlands
  • 2Laboratoire de Chimie, École Normale Supérieure de Lyon, 69364 Lyon CEDEX 07, France
  • 3Van ’t Hoff Laboratory for Physical and Colloid Chemistry, Department of Chemistry & Debye Institute for Nanomaterials Science, Utrecht University, Padualaan 8, 3584 CH Utrecht, Netherlands
  • 4Laboratoire de Physique des Solides—UMR 8502, CNRS & Université Paris-Saclay, 91405 Orsay, France

  • *r.tuinier@tue.nl

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Vol. 125, Iss. 12 — 18 September 2020

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