Effect of Disparity in Self Dispersion Interactions on Phase Behaviors of Molten A-b-B Diblock Copolymers.

Abstract

Phase behaviors of molten A-b-B diblock copolymers with disparity in self dispersion interactions are revisited here. A free energy functional is obtained for the corresponding Gaussian copolymers under the influence of effective interactions originating in the localized excess equation of state. The Landau free energy expansion is then formulated as a series in powers of A and B density fluctuations up to 4th order. An alternative and equivalent Landau energy is also provided through the transformation of the order parameters to the fluctuations in block density difference and free volume fraction. The effective Flory χ is elicited from its quadratic term as the sum of the conventional enthalpic χH and the entropic χS that is related to energetic asymmetry mediated by copolymer bulk modulus. It is shown that the cubic term is balanced with Gaussian cubic vertex coefficients in corporation with energetics to yield a critical point at a composition rich in a component with stronger self interactions. The full phase diagrams with classical mesophases are given for the copolymers exhibiting ordering upon cooling and also for others revealing ordering reversely upon heating. These contrasting temperature responses, along with the skewness of phase boundaries, are discussed in relation to χH and χS. The pressure dependence of their ordering transitions is either barotropic or baroplastic; or anomalously exhibits anomalously both at different stages. These actions are all explained by the opposite responses of χH and χS to pressure.