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The weight-average molecular weight Mw, z-average radius of gyration Rg, and second virial coefficient A2 have been determined between 15 and 52°C for dilute aqueous solutions of methylcellulose (MC) with three different molecular weights and constant degree of substitution (DS) of 1.8 using static light scattering. These measurements, conducted within 1 h of heating the homogeneous solutions from 5°C, reveal that the theta temperature for MC in water is Tθ = 48 ± 2°C, with A2 < 0 for T > Tθ, indicative of lower critical solution temperature (LCST) behavior. However, after annealing a solution for 2 days at 40°C evidence of high molecular weight aggregates appears through massive increases in the apparent Mw and Rg, a process that continues to evolve for at least 12 days. Cryogenic transmission electron microscopy images obtained from a solution aged for 3 weeks at 40°C reveal the presence of micron size fibrils with a diameter of 16 ± 4 nm, structurally analogous to the fibrils that form upon gelation of aqueous MC solutions at higher concentrations and elevated temperatures. Growth of fibrils from a solution characterized by a positive A2 indicates that semiflexible MC dissolved in water is metastable at T < Tθ, even though the solvent quality is apparently good. The minimum temperature required for MC solutions to aggregate is estimated to be 30°C, based on the rate-independent gel-to-solution transition determined by small-amplitude oscillatory shear measurements conducted while cooling 0.5 and 5.0 wt % solutions. These results cannot be explained based solely on separation into two isotropic phases upon heating using classical Flory-Huggins solution theory. We speculate that the underlying equilibrium phase behavior of aqueous MC solutions involves a nematic order parameter.
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© 2015 American Chemical Society.
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- Period 2