Shear alignment and realignment of sphere-forming and cylinder-forming block-copolymer thin films

In common with many other structured fluids, block copolymers can be effectively oriented by shear. This susceptibility to shear alignment has previously been shown to hold even in thin films, containing as few as two layers of spherical microdomains, or even a single layer of cylindrical microdomains. A phenomenological model has been proposed to describe the alignment of such block-copolymer films, yielding the microdomain lattice order parameter as a function of shearing temperature, stress, and time. Here we directly test the central idea of that model, that the grains which are most misaligned with the shear direction are selectively destroyed, to reform in a direction more closely aligned with the shear. Films are first shear aligned from a polygrain state into a monodomain orientation and are then subjected to a second shear, at a variable stress (σ) and misorientation angle (δθ) relative to the monodomain director, allowing the effects of σ and δθ to be independently and systematically probed. For both cylinder-forming and sphere-forming block copolymers, these experiments confirm the basic premise of the model, as the stress required for realignment increases monotonically as δθ becomes smaller. For a cylinder-forming block copolymer, we find that the characteristic stress σc required to realign cylinders from one monodomain orientation to another is indistinguishable from that required to generate a monodomain orientation from the polygrain state. By contrast, the hexagonal lattice of spheres requires a value of σc more than 3 times as high for reorientation than for generation of the initial monodomain orientation.