Polymer Engineering Faculty Research


Unexpected Scaling Behavior of the OrderâDisorder Transition of Nearly Symmetric Polystyrene-block-polyisoprene Diblock Copolymers Dilated with a Nominally Neutral Solvent at Very Low Dilution

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Publication Date

Fall 2009


The scaling behavior of the order−disorder transition (ODT) temperature for several nearly symmetric P(S-b-I) copolymers has been studied over a polymer volume fraction range of 0.9 ≤ diblock ≤ 1. To enable precise control of the concentration at high and at elevated temperatures as the concentration approaches the neat melt, compressed CO2 is used as the diluent in place of more traditional liquid solvents. Swelling of polymer films by CO2 over the concentration range of interest was determined using high-pressure ellipsometry, while high-pressure static birefringence measurements were used to determine the location of the ODT in dilated bulk samples. Log−log plots of χODT vs diblock allowed the determination of the scaling parameter, α, for comparison with the dilution approximation. At polymer volume fractions between 0.88 and 0.98, α varied between −1.2 and −1.3, which is consistent with scaling for neutral liquid diluents. At very low dilution, however, the scaling changes abruptly, and unusually high scaling parameters are observed for all copolymers at nearly identical polymer concentrations. This behavior suggests that solvent is initially segregating at the interface before beginning to distribute throughout the polymer. These data further illustrate the inadequacies of the dilution approximation (mean field) to correctly predict the ODT temperature, especially at very high polymer concentrations.



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