Surface Charges Control the Structure and Properties of Layered Nanocomposite of Cellulose Nanofibrils and Clay Platelets

[Image: see text] The interfacial bonding and structure at the nanoscale in the polymer–clay nanocomposites are essential for obtaining desirable material and structure properties. Layered nanocomposite films of cellulose nanofibrils (CNFs)/montmorillonite (MTM) were prepared from the water suspensions of either CNFs bearing quaternary ammonium cations (Q-CNF) or CNFs bearing carboxylate groups (TO-CNF) with MTM nanoplatelets carrying net surface negative charges by using vacuum filtration followed by compressive drying. The effect of the ionic interaction between cationic or anionic charged CNFs and MTM nanoplatelets on the structure, mechanical properties, and flame retardant performance of the TO-CNF/MTM and Q-CNF/MTM nanocomposite films were studied and compared. The MTM nanoplatelets were well dispersed in the network of TO-CNFs in the form of nanoscale tactoids with the MTM content in the range of 5–70 wt %, while an intercalated structure was observed in the Q-CNF/MTM nanocomposites. The resulting TO-CNF/MTM nanocomposite films had a better flame retardant performance as compared to the Q-CNF/MTM films with the same MTM content. In addition, the effective modulus of MTM for the TO-CNF/MTM nanocomposites was as high as 129.9 GPa, 3.5 times higher than that for Q-CNF/MTM (37.1 GPa). On the other hand, the Q-CNF/MTM nanocomposites showed a synergistic enhancement in the modulus and tensile strength together with strain-to-failure and demonstrated a much better toughness as compared to the TO-CNF/MTM nanocomposites.