Cellulose nanocrystals (CNCs) are of increasing interest for packaging applications because of their biodegradability, low cost, high crystallinity, and high aspect ratio. The objective of this study was to use positron annihilation lifetime spectroscopy (PALS) to investigate the free volume of CNC films with different structural arrangements (chiral nematic vs shear-oriented CNC films) and relate this information to gas barrier performance. It was found that sheared CNC films with higher CNC alignment have lower free volume and hence have more tortuosity than chiral nematic self-assembled films, which lowers gas diffusion throughout the films. The overall barrier performance of the aligned CNC film obtained in this study has a higher barrier performance than high barrier polymer films like PVOH and EVOH. Furthermore, a modified model was developed for single-component CNC films to predict the gas permeability with variation of CNC alignment with validation by the data taken.
Keywords: alignment; cellulose nanocrystal; free volume; gas barrier; gas diffusion; permeability.