Phase behaviour of PMMA-b-PHEMA with solvents methanol and THF: modelling and comparison to the experiment.

Self-consistent field theory is used to model the self-assembly of a symmetric PMMA-block-PHEMA in the presence of two solvents, methanol and tetrahydrofuran (THF). The model predictions are compared to our experimental results of solvent-vapour annealing of thin polymer films, where the sequence of cylinder to gyroid (or micelles) to lamellar phases was found upon increasing the methanol-THF ratio and for particular extents of film swelling. The Hansen solubility parameters are used to estimate the Flory-Huggins interaction parameters (χ) needed in the theoretical model. However, because enacting the experimental range of high (χ)N values is computationally prohibitive, the use of moderate (χ)N values is compensated by employing larger values of the solvent-to-polymer size ratio (α). This approach is validated by showing that the predicted phase diagrams exhibit qualitatively similar trends whether (χ)N or α is increased. Using such an approach, the theory predicts a cylinder to gyroid to lamellar transition on increasing the THF-methanol ratio, a trend consistent with that observed in the experiments.