Self-assembly behavior and adhesive performance of imidazolium cation grafted cellulose nanocrystals in confined space

Confined evaporation-induced self-assembly (C-EISA) is a powerful technique to guide disordered nanoparticles into long-range organized structures. Herein, we investigate the C-EISA behavior of 1-butyl-3-vinylimidazolium cation ([VBIm]+) grafted cellulose nanocrystals (CNC-C) in a parallel-plates confined geometry. Interestingly, CNC-C can spontaneously assemble into maze-like patterns with branch dimensions on the order of micrometers and uniformly distributed throughout the confined space, which is completely different from the lamellar self-assembly patterns of unmodified CNCs. Combining in situ observations and microscopic characterization, we speculate that the formation of maze-like patterns originates from the reduction of colloidal stability induced by the grafted imidazolium cations. The electrostatic attraction between CNC-C aggregated bundles and glass substrates acts as anchor points, thereby leading to the unstable motion of the liquid-air menisci during the inward intrusion of air. Due to the physicochemical properties and unique C-EISA behavior, the CNC-C based adhesive can maintain adhesion at temperatures of ca. 200 °C, while rapidly debonding when immersed in water, demonstrating the potential to be used as stimuli-responsive temporary or removable adhesives. Furthermore, the strategy proposed in this work for achieving CNCs patterning is also promising to be extended to other anisotropic rod-shaped nanoparticles.