The approach to asymptotic critical behavior in polymer solutions is governed by a competition between the correlation length of critical fluctuations diverging at the critical point of phase separation and an additional mesoscopic length scale, the radius of gyration. In this paper we present a theory for crossover between two universal regimes: a regime with Ising (fluctuation-induced) asymptotic critical behavior, where the correlation length prevails, and a mean-field tricritical regime with theta-point behavior controlled by the mesoscopic polymer chain. The theory yields a universal scaled description of existing experimental phase-equilibria data and is in excellent agreement with our light-scattering experiments on polystyrene solutions in cyclohexane with polymer molecular weights ranging from up to . The experiments demonstrate unambiguously that crossover to theta-point tricriticality is controlled by a competition of the two mesoscales. The critical amplitudes deduced from our experiments depend on the polymer molecular weight as predicted by de Gennes [Phys. Lett. 26A, 313 (1968)]. Experimental evidence for the presence of logarithmic corrections to mean-field tricritical theta-point behavior in the molecular-weight dependence of the critical parameters is also presented.
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22 October 2005
Research Article|
October 24 2005
Competition of mesoscales and crossover to theta-point tricriticality in near-critical polymer solutions
M. A. Anisimov;
M. A. Anisimov
a)
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology,
University of Maryland
, College Park, Maryland 20742
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A. F. Kostko;
A. F. Kostko
b)
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology,
University of Maryland
, College Park, Maryland 20742
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J. V. Sengers;
J. V. Sengers
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology,
University of Maryland
, College Park, Maryland 20742
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I. K. Yudin
I. K. Yudin
c)
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology,
University of Maryland
, College Park, Maryland 20742
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
b)
Also at St. Petersburg State University of Refrigeration and Food Engineering, St. Petersburg, 191002, Russia.
c)
Permanent address: Oil and Gas Research Institute, Russian Academy of Sciences, Moscow, 117971, Russia.
J. Chem. Phys. 123, 164901 (2005)
Article history
Received:
August 01 2005
Accepted:
August 16 2005
Citation
M. A. Anisimov, A. F. Kostko, J. V. Sengers, I. K. Yudin; Competition of mesoscales and crossover to theta-point tricriticality in near-critical polymer solutions. J. Chem. Phys. 22 October 2005; 123 (16): 164901. https://doi.org/10.1063/1.2056543
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