Surface C6-carboxylated cellulose nanofibrils (TCNF-COONa) were prepared from wood cellulose by TEMPO/NaBr/NaClO oxidation in water at pH 10 and successive mechanical disintegration of the oxidized cellulose in water. Aqueous TCNF dispersions with magnesium and calcium carboxylate groups, TCNF-COOMg and TCNF-COOCa, respectively, were prepared in high yields of 85–90% from aqueous TCNF-COONa dispersion by addition of aqueous MgCl2 and CaCl2 solutions, respectively, to the aqueous TCNF-COONa dispersion, washing the gels with water by filtration without drying, and successive mechanical disintegration of the gels in water. The cast-dried TCNF-COONa, TCNF-COOMg, and TCNF-COOMg films had no significant differences in density and water content at 23 °C and 50% relative humidity. Consequently, they had similar mechanical properties. Aqueous TCNF-COONa/Mg and TCNF-COONa/Ca dispersions were prepared by mixing TCNF-COONa and either TCNF-COOMg or TCNF-COOCa dispersion at a weight ratio of 1:1. Oxygen permeabilities of the TCNF-COONa/Mg and TCNF-COOCa films had the lowest and highest values at 50% RH, respectively, while those of the TCNF-COOMg and TCNF-COONa/Ca films had the lowest and highest values at 80%, respectively. The Na and Mg counterions in the aqueous TCNF-COONa/Mg dispersion were homogeneously distributed in each TCNF element without separately keeping individual TCNF-COONa and TCNF-COOMg elements.
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