Abstract
The thermodynamics of formation of “crew-cut” micelles of polystyrene-block-poly(acrylic acid) (PS-b-PAA) diblock copolymers were investigated. The PAA/PS ratios were in the range 0.08−0.33, and N,N-dimethylformamide/water (DMF/H2O) mixtures were used as the selective solvent. For the block ratios investigated here, the copolymers form spherical crew-cut micelles with a large PS core and a thin PAA corona. The temperature dependence of the critical micelle concentration (cmc) was determined under different conditions from scattered light intensity measurements as a function of temperature. The closed association model was found to describe the micellization process and was used to calculate the standard Gibbs free energies (ΔG°), the standard enthalpies (ΔH°), and the standard entropies (ΔS°). The effects of solvent composition, copolymer composition, and added NaCl content on the thermodynamic functions were studied. From the experimental data, a single set of combined equations for the standard thermody...
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