Hydrophobic, Ductile, and Transparent Nanocellulose Films with Quaternary Alkylammonium Carboxylates on Nanofibril Surfaces

Hydrophobic, ductile, and transparent nanocellulose films were prepared by casting and drying aqueous dispersions of 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibrils (TOCNs) with quaternary alkylammoniums (QAs) as counterions for the surface carboxylate groups. TOCN films with tetramethylammonium and tetraethylammonium carboxylates showed high optical transparencies, strain-to-failure values (14-22%), and work-of-fracture values (20-27 MJ m(-3)). The ductility of these films was likely caused by the alkyl chains of the QA groups densely covering the TOCN surfaces and being present at the interfaces between the TOCN elements in the films. The water contact angle of the TOCN-QA films increased to ∼100° by introducing tetra(n-butyl)ammonium groups as counterions. Thus, TOCN film properties can be controlled by changing the chemical structure of the counterions from Na to QAs. The hydrophilic TOCN surfaces can be changed to hydrophobic simply and efficiently by the conversion from TOCN-Na to TOCN-QA, when TOCNs are used as nanofillers in hydrophobic polymer matrices.