Macromolecules, Vol.27, No.15, 4063-4075, 1994
The Gyroid - A New Equilibrium Morphology in Weakly Segregated Diblock Copolymers
We report the identification of a new equilibrium microdomain morphology in an intermediate to weakly segregated diblock copolymer melt. A polystyrene-polyisoprene (SI) diblock copolymer consisting of 37 wt % styrene and of total M(w) = 27 400 was observed to transform from the lamellar morphology (in equilibrium at low annealing temperatures) to a new morphology at annealing temperatures approximately 50-degrees-C below the order-disorder transition (ODT). The transformation was observed to be thermoreversible. investigation of the new morphology via small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) revealed the new structure to have remarkable three-dimensional long-range order, to belong to the cubic space group Ia3d, and to possess a bicontinuous cubic microstructure. From computer simulations of model structures and comparison with microscopy results, we propose models for the new morphology based on the triply periodic G minimal surface (gyroid) discovered by Schoen;1 similar morphologies have been observed in a variety of microphase-separated surfactant-water systems. Blends of this diblock with various short-chain homopolymers were used to investigate the compositional extent of the region of Ia3d stability on the phase diagram; the results indicate that the Ia3d phase is stable over a wide range of minority component volume fractions.
Keywords:MICRODOMAIN MORPHOLOGY;BLOCK COPOLYMERS;HOMOPOLYMER BLENDS;BINARY BLENDS;CUBIC PHASES;SURFACES;STYRENE;SYSTEMS