Self-assembly behaviors of colloidal cellulose nanocrystals: A tale of stabilization mechanisms

In solvent casting, colloidal nanocrystal self-assembly patterns are controlled by a mix of cohesive and repulsive interactions that promote destabilization-induced self-assembly (DISA) or evaporation-induced self-assembly (EISA). Tuning the strength and nature of the stabilization mechanisms may allow repulsive interactions to govern self-assembly during the casting of colloidal cellulose nanocrystal (CNC) suspensions.

We propose a tool to classify the level of electrostatic and solvation-induced stabilizations based on two solvent parameters only: dielectric constant, ε, and chemical affinity for CNCs, in terms of Hansen Solubility Parameters, R_a. These criteria are applied to study CNC self-assembly in solvent casting experiments in various media and binary mixtures.

In solvent casting of suspensions stabilized through a combination of electrostatic and solvation effects, the primarily governing mechanism is EISA, which leads to the formation of chiral nematic domains and optically active thin films. In electrostatically-stabilized suspensions, EISA and DISA are in competition and casting may yield anything from a continuous film to a powder. In other suspensions, DISA prevails and evaporation yields a powder of CNC agglomerates. By classifying media according to their stabilization mechanisms, this work establishes that the behavior of CNC suspensions in solvent casting may be predicted from solvent parameters only.