From Chitin Nanowhisker Colloidal Dispersions to Anisotropic Microfibers: Structural Evolution in Its Transformation Process as Revealed by Synchrotron Wide-Angle X-ray Diffraction Measurements.

Abstract

Nanowhiskers in a colloidal dispersion are known to form chiral nematic liquid crystals (CNLC), as seen in a cellulose nanowhisker or so-called cellulose nanocrystal and chitin nanowhisker. In our related work, we clarified that once the thus-created chitin nanowhiskers with surface modified by chitosan (CTWK-CS) in CNLC phase were wet-spun, we could directly obtain anisotropic microfibers containing the highly ordered CTWK-CS. This drastic structural transformation from CNLC to anisotropic microfibers might relate to several important stages, i.e., stage (i) is the alignment of CTWK-CS initiated by a specific concentration and flow to create aggregation in the CNLC state, stage (ii) is the coagulation of CTWK-CS in CNLC to transform to microfibers, and stage (iii) is the drying of the thus-extruded microfibers to allow CTWK-CS alignment. The present work sets up the experimental systems simulating stages (i) and (iii) to reveal the orientational behavior of CTWK-CS and the structural evolution, respectively, by synchrotron 2D WAXD measurement. In stage (i), the high degree of the parallel alignments of CTWK-CS with the chain axis oriented along the flow direction of the colloidal dispersions confirms that the flow and concentration synergistically controlled CTWK-CS alignment. In contrast, for stage (iii), the poor c-axial orientation of CTWK-CS in as-spun wet microfibers gradually changed to the high degree of c-axial orientation along the fiber direction during drying process, indicating a reorientation of CTWK-CS along with dehydration. The present study declares an in situ observation of the direct wet spinning of nanowhiskers about their remarkable alignments in the sheared colloidal dispersions (stage (i)) and their random-to-high reorientation during the drying process of the as-spun wet microfiber (stage (iii)).