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Competition of mesoscales and crossover to tricriticality in polymer solutions

М. А. АнисимовDepartment of Chemical Engineering and Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742, USAA. F. KostkoDepartment of Chemical Engineering and Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742J. V. SengersDepartment of Chemical Engineering and Institute for Physical Science and Technology, University of Maryland, College Park, Maryland 20742
2002en
ABI

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We show that the approach to asymptotic fluctuation-induced critical behavior in polymer solutions is governed by a competition between a correlation length diverging at the critical point and an additional mesoscopic length-scale, the radius of gyration. Accurate light scattering experiments on polystyrene solutions in cyclohexane with polymer molecular weights ranging from 200 000 up to 11.4x10(6) clearly demonstrate a crossover between two universal regimes: a regime with Ising asymptotic critical behavior, where the correlation length prevails, and a regime with tricritical theta-point behavior determined by a mesoscopic polymer-chain length.

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