Mesophase characteristics of cellulose nanocrystal films prepared from electrolyte suspensions

Cellulose nanocrystals (CNCs) exhibit a cholesteric mesophase above a critical concentration in aqueous suspensions. Above this concentration, CNCs self-organize into left-handed helicoidal structures that can be preserved in dried, stratified films. In this systematic study, we have prepared optically-active CNC films cast from different electrolyte suspensions and investigated, via circular dichroism and other techniques, the effects of counterion type (six mono/divalent salts, including those responsible for promoting "salting-out" and "salting-in" in the Hofmeister series) and ionic strength on mesomorphic behavior and cholesteric arrangement. The presence of electrolytes influences CNC colloidal stability by compressing the electric double layer and altering interactions among neighboring CNCs and water, thereby affecting the extent to which the CNCs form a mesophase. Interestingly, mesomorphic behavior and CNC alignment appear to be sensitive to cationic radius and charge valence, in which case the optical properties of CNC films can be adjusted for targeted sustainable applications. Such heuristic rules can be valuable for predicting the stability and characteristics of CNC microstructure in designer coatings and thin films prepared by introducing suitable cations prior to film formation.