Multiscale study of the chiral self-assembly of cellulose nanocrystals during the frontal ultrafiltration process

The structural organization of cellulose nanocrystal (CNC) suspensions at the membrane surface during frontal ultrafiltration has been characterized, for the first time, at the nano- and microscale by in situ small-angle X-ray and light scattering (SAXS and SALS, respectively). During filtration, the particles assembled at the membrane surface and formed the so-called concentration polarization layer (CPL), which contains CNCs arranged in a chiral nematic (cholesteric) helicoidal structure, with the long axis of the CNCs oriented parallel to the membrane surface, and the helical axis of the cholesteric structure oriented perpendicular to the membrane surface. The self-organization of CNCs in the form of oriented cholesteric structures was further characterized by a pitch gradient in the CPL. The structure of the CPL was also investigated upon release of the transmembrane pressure. SAXS data revealed a relaxation process associated with a diffusion of the CNCs from the membrane surface towards the bulk, while SALS measurements revealed a re-organization of the cholesteric phase that was preserved all along the deposit. The preservation of the observed structure after 14 days of continuous filtration followed by air-drying was confirmed using scanning electron microscopy and wide-angle X-ray diffraction, demonstrating the feasibility of the process scale-up.