Self-assembly of block copolymers during hollow fiber spinning: an in situ small-angle X-ray scattering study

We investigated the self-assembly of block copolymers during hollow fiber membrane (HFM) fabrication by conducting in situ small angle X-ray scattering (SAXS) and ex situ scanning electron microscopy (SEM) studies. SAXS enables us to follow the structural rearrangements after extrusion at different distances from the spinning nozzle. The kinetics of the spinning process is examined as a function of the composition of block copolymer solutions and the spinning parameters. We studied the influence of the extrusion rate on the block copolymer microdomains and their self-assembly in weakly segregated and ordered solutions. The addition of magnesium acetate (MgAc2) leads to the ordering of micelles in the block copolymer solution already at lower polymer concentrations and shows an increased number of micelles with larger domain spacing as compared to the pristine solution. The SAXS data show the effect of shear within the spinneret on the self-assembly of block copolymers and the kinetics of phase separation after extrusion. It is observed that the ordering of micelles in solutions is decreased as indicated by the loss of crystallinity while high extrusion rates orient the structures perpendicular to the fiber direction. The structural features obtained from in situ SAXS experiments are correlated to the structure in the block copolymer solutions in the absence of shear and the morphologies in flat sheet and HF membranes obtained by ex situ SEM. This allows a systematic and comparative study of the effects varying the microdomain ordering within different block copolymer solutions and the formed membrane structures.