Finding Simplicity in Complexity: Scaling, Tricriticality, and Crossover in Polymer Solutions
Mikhail A. Anisimov, Chemical and Biomolecular Engineering, University of Maryland, Building 085, University of Maryland, College Park, MD 20742 and Jan V. Sengers, Institute for Physical Science and Technology, University of Maryland, Building 090, University of Maryland, College Park, MD 20742

Generalizing a scaled universal description of phase separation in polymer solutions proposed by Benjamin Widom, we have develop a scaled representation of coexistence curves, osmotic sussceptibilities, and correlation lengths that accounts for a crossover between a regime with Ising (fluctuation-induced) asymptotic critical behavior, where the correlation length of the critical fluctuations prevails, and a mean-field tricritical regime with theta-point behavior controlled by the mesoscopic polymer chain. In particular, we have clarified a connection between traditional themodynamics of polymer solutions and de Gennes-Widom's scaling approach. The crossover theoretical description is compared with experimental data on liquid-liquid phase-equilibria and light-scattering measurements of susceptibilities and correlation lengths. In addition, we demonstrate the validity of de Gennes' prediction for the molecular-weight scaling of the critical amplitudes.

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Polymer Thermodynamics I

The Preliminary Program for 2005 Annual Meeting (Cincinnati, OH)