Cellulose nanofibers (CNFs) containing ammonium carboxylate groups are possibly converted to CNFs with protonated carboxy groups via simple thermal decomposition. The CNF-COOH structures in films and composites can form intra- and inter-fibrillar hydrogen bonds, which are expected to enhance mechanical, thermal, and gas-barrier properties. In this study, CNF pellets and films containing ammonium carboxylate groups were first prepared and subjected to dry thermal, humid thermal, and hydrothermal treatments to clarify the convertibility of ammonium carboxylate groups to protonated ones, considering simple thermal processes to improve CNF properties. The ratios of ammonium carboxylate or protonated carboxy groups in the heated samples were determined from their infrared spectra. Freeze-dried pellets-COONH4 and cast/dried CNF-COONH4 films contained 81–82% ammonium carboxylate group ratios before heating; however, complete formation of ammonium carboxylate groups in the pellet and film samples could not be achieved. Heating at 90 °C and 90% RH for 240 min was required for the CNF-COONH4 films to reduce the ammonium carboxylate ratio from 81% to 8%. These results indicate that the ammonium carboxylate groups in the film samples exhibited high resistance to the formation of protonated carboxy groups under the thermal conditions applied. Consequently, it is not plausible that CNF-COONH4 films were mostly converted to CNF-COOH structures under the heating conditions used in this study over a short time. Nevertheless, partial conversions of CNF-COONH4 groups to CNF-COOH ones by thermal treatment under suitable conditions are regarded as simple processes to change the structures of counterions of carboxy groups and resultant film properties.
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