Dynamics of Shear-Induced Alignment of a Lamellar Diblock:  A Rheo-optical, Electron Microscopy, and X-ray Scattering Study

Abstract

In-situ rheo-optical methods are used to guide electron microscopy (TEM) and X-ray scattering (SAXS) studies of structure development during flow-induced alignment in a lamellar block copolymer melt (nearly symmetric polystyrene−polyisoprene diblock, ODT ≃ 172 °C). The progress of shear-induced alignment is recorded in real-time using flow birefringence; at selected points during alignment samples are taken for ex-situ characterization by TEM and SAXS along all three axes (v, ∇v, ∇ × v) of the flow geometry. Three different trajectories are examined:  perpendicular alignment and two qualitatively different routes to parallel alignment in the high-frequency regime (ω > ω'_c). In general, the initial “fast” process not only enhances the projection of the orientation distribution that corresponds to the final state but also increases other projections of the distribution; the late-stage “slow” process eliminates these other projections and perfects a single alignment. For example, the highest frequency path to parallel alignment begins by transforming poorly organized regions into layers that are predominantly oriented along the parallel and transverse directions. The transition to the slow process is marked by the development of a characteristic texture in which tilt wall boundaries normal to the flow direction separate bands that form a repeating “chevron” pattern (layers tilted up and down about the ∇×v axis). The coarsening of this pattern dominates the slow process, during which the transverse projection is also eliminated