Cellulose-layered montmorillonite (MMT) nanocomposites were prepared by precipitation from N-methylmorpholine-
N-oxide (NMMO)/water solutions. Two hybrid samples were obtained to investigate the influence of the
reaction time on the extent of clay dispersion within the matrix. It was observed that longer contact times are
needed to yield nanocomposites with a partially exfoliated morphology. The thermal and thermal oxidative properties
of the hybrids, which might be of interest for fire-resistant final products, were investigated by thermogravimetry
and chemiluminescence (CL). The nanocomposites exhibited increased degradation temperatures compared to
plain cellulose, and the partially exfoliated sample showed the maximum stability. This result was explained in
terms of hindered transfer of heat, oxygen, and degraded volatiles due to the homogeneously dispersed clay filler.
Kinetic analysis of the decomposition process showed that the degradation of regenerated cellulose and cellulosebased
hybrids occurred through a multistep mechanism. Moreover, the presence of nanoclay led to drastic changes
in the dependence of the activation energy on the degree of degradation. CL analysis showed that longer permanence
in NMMO/water solutions brought about the formation of carbonyl compounds on the polymer backbone. Moreover,
MMT increased the rate of dehydration and oxidation of cellulose functional moieties. As a consequence, cellulose
was found to be less stable at temperatures lower than 100 °C. Conversely, at higher temperatures, the hindering
of oxygen transfer prevailed, determining an increase in thermo-oxidative stabilit
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