Orientation behavior of AB and ABC block copolymers under large amplitude oscillatory shear flow

Flow alignment in a large amplitude oscillatory shear field (LAOS) of a lamellar AB and a lamellar ABC block copolymer (A,B are lamellae, C forms cylinders in B-lamellae) has been studied. 2D-small angle X-ray scattering (2D-SAXS) and scanning electron microscopy were used for morphological characterization, and flow birefringence and Fourier-Transform rheology were used to monitor the orientation. The diblock copolymer shows the known frequency-dependent orientation behavior, i.e., a perpendicular or a parallel orientation of the lamellae, while under all conditions for the ABC block copolymer only a perpendicular orientation after a long induction period was found. Due to the introduced third block C the AB lamellar structure with a high viscosity contrast between the A and B domains cannot adapt a parallel orientation of sliding phases. Dynamic mechanical analysis indicates shear induced improvement of the microphase separation of the short C block.