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The physicochemical characteristics of commercially available CAB in solvent-cast films, with a focus on their microstructural features, were investigated via XRD, SEM, AFM, and TOPEM DSC analysis in this study. The number of hydroxyl groups predominantly dictates the film-forming capacity, while the type and placement of side groups on the cellulose backbone determine the films' semi-crystallinity. In films showing signs of potential cholesteric ordering, increased hydroxyl