Using Rheology and Image Processing to Study the Effects of Cellulose Nanocrystal Sedimentation.

The effect of sedimentation on lyotropic liquid crystalline dispersions is both an interesting subject in colloidal science and is of practical importance for understanding changes that can occur during dispersion storage. This research explored how the seemingly subtle changes in average length resulting from a single sedimentation step affected the rheological properties and self-assembly of aqueous dispersions of sulfated cellulose nanocrystals. Sedimentation of a primarily isotropic aqueous cellulose nanocrystal dispersion for 1 month at ambient conditions resulted in an isotropic top phase and a biphasic bottom phase, which were separated for further study. Both atomic force microscopy measurements and intrinsic viscosities determined via Fedor's equation showed preferential fractionation of longer cellulose nanocrystals (CNCs) to the bottom phase. The effects of this fractionation on dispersion rheology and phase behavior were studied by preparing a range of concentrations from each phase. As expected, the concentration for the isotropic-biphasic phase transition was significantly lower for the bottom phase than for the top phase or parent dispersion. Rheological changes were generally subtle, but significant differences were seen in the storage modulus at concentrations approaching rheological gelation. Most notably, quantitative image processing showed that even this simple, single-step fractionation process had a significant impact on the relative proportion of tactoids and chiral helices with planar and homeotropic anchoring in self-assembled cellulose nanocrystal films. These results highlight the impact that changes in polydispersity due to sedimentation can have on the self-assembly of nanomaterial mesogens.