Once-dried 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibril (TOCN) films with sodium carboxylate groups (TOCN-COONa) were soaked in aqueous MgCl2, CaCl2, AlCl3 and FeCl3 solutions to change the counterion to TOCNs-COOM films (M: metal ion). Dry TOCN-COOM films had high Young's moduli (11-20GPa) and tensile strength (170-280MPa). In particular, the wet TOCN films with aluminum and iron (III) carboxylates had high Young's moduli and tensile strengths of ~3GPa and 30-40MPa, respectively, even at water contents of ~470%. Moreover, the dry TOCN films with calcium and aluminum carboxylates had extremely low oxygen permeabilities of 0.08 and 0.15mLμmm-2day-1kPa-1, respectively, even at 80% relative humidity, which are outstanding values compared to those of other films reported previously. These results are explained in terms of the high water resistance of the films, which is caused by the formation of interfibrillar cross-linkages through multivalent metal ions.
Shimizu, M., Saito, T., & Isogai, A. (2016). Water-resistant and high oxygen-barrier nanocellulose films with interfibrillar cross-linkages formed through multivalent metal ions. Journal of Membrane Science, 500, 1–7. https://doi.org/10.1016/j.memsci.2015.11.002