Journal
MACROMOLECULES
Volume 43, Issue 15, Pages 6476-6484Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma101031t
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- The Netherlands Organisation for Scientific Research (NWO) [021.002.013]
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When oppositely charged polyelectrolytes arc mixed below a critical salt concentration, their mixtures show macroscopic phase separation into a dilute and a dense, polyclectrolyte complex phase. Binodal compositions of the polyelcctrolyte complexes have been measured experimentally using fluorescently labeled polyclectrolytes. We used fluorescein-labeled poly(acrylic acid) (PAA) of four different chain lengths (N = 20, 50, 150, and 510) to determine the binodal compositions of polyelectrolyte complexes of PAA and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) of similar chain lengths. The water content of polyelectrolyte complexes obtained has a lower limit of about 65%, practically independent of chain length, and increases with increasing salt concentration. We interpret our results on binodal compositions, water content and critical salt concentration as a function of chain length using the mean-field model of Voorn and Overbeek and find good quantitative agreement with our experiments using only one adjustable parameter. We believe that such a model can be used to predict equilibrium concentrations also for other strongly charged flexible polyelectrolytes.
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