Evolution of a dispersed morphology from a co-continuous morphology in immiscible polymer blends

Abstract

We observed, via transmission electron microscopy, the evolution of a dispersed morphology from a modulated co-continuous morphology in immiscible blends of two amorphous polymers, poly(methyl methacrylate) (PMMA) and polystyrene (PS). Upon rapid precipitation of a homogeneous solution, which can be regarded as being equivalent to spinodal decomposition via temperature quenching, we observed a modulated co-continuous morphology for all three blend compositions, 70/30, 50/50, and 30/70 PMMA/PS blends. This observation is interpreted with the Cahn's linearized theory, which has been found to be accurate in describing phase separation in the early stage of spinodal decomposition. When a rapidly precipitated PMMA/PS blend specimen having asymmetric (70/30, 60/40, 55/45 or 30/70) blend composition was annealed under isothermal conditions at 170°C for varying periods, the modulated co-continuous morphology evolved into a dispersed morphology, in which the major component formed the continuous phase and the minor component formed the discrete phase, and into a `dual mode' of dispersed morphology in the symmetric (50/50) PMMA/PS blend. This observation is interpreted in terms of the percolation-to-cluster transition mechanism proposed by Hashimoto and co-workers. The morphology evolution, during isothermal annealing, of a rapidly precipitated blend may be regarded as being equivalent to late stages of spinodal decomposition, which is controlled by diffusion and coalescence. The rate of morphology development in PMMA/PS blend during isothermal annealing was found to depend on the zero-shear viscosity ratio of the constituent components. This observation is interpreted in terms of Siggia's theory for late stages of spinodal decomposition.