Liquid-crystalline assembly of spherical cellulose nanocrystals

Rod-shaped cellulose nanocrystals (CNCs), also called cellulose nanorods (CNRs), possess anisotropic properties that allow for their self-organization into chiral nematic liquid crystals. Interestingly, spherical cellulose nanocrystals (cellulose nanospheres, CNSs) have also been shown to form a chiral liquid-crystalline phase in recent years. Herein, to understand how the similar assembly takes places as particle dimension changes, the organization features of CNSs were investigated. Results of this study demonstrate that above a critical concentration in suspension, CNSs organize into a liquid-crystal phase consisting of periodically parallel-aligned layer structures. This structure persists after suspension drying. In comparison with CNRs, the alignment of CNSs exhibits a shorter layer distance, lower order degree, and weaker long-range orientation. To explain the early stages of tactoid formation, a “caterpillar-like” model was proposed, which was captured by freezing the CNS suspension in an intermediate aggregation state. This structure serves as the fundamental unit for further liquid-crystal assembly.