Tuning the Nanoscale Properties of Phosphorylated Cellulose Nanofibril-Based Thin Films To Achieve Highly Fire-Protecting Coatings for Flammable Solid Materials

Ultrathin nanocomposite films were prepared by combining cellulose nanofibrils (CNFs) prepared from phosphorylated pulp fibers (P-CNF) with montmorillonite (MMT), sepiolite (Sep) clay, or sodium hexametaphosphate (SHMP). The flame-retardant and heat-protective capability of the prepared films as casings for a polyethylene (PE) film was investigated. Heating the coated PE in air revealed that the polymer film was thoroughly preserved up to at least 300 °C. The P-CNF/MMT coatings were also able to completely prevent the ignition of the PE film during cone calorimetry, but neither the P-CNF/Sep nor the P-CNF/SHMP coating could entirely prevent PE ignition. This was explained by the results from combined thermogravimetry Fourier transform infrared spectroscopy, which showed that the P-CNF/MMT film was able to delay the release of PE decomposition volatiles and shift its thermal degradation to a higher temperature. The superior flame-retardant performance of the P-CNF/MMT films is mainly attributed to the unique compositional and structural features of the film, where P-CNF is responsible for increasing the char formation, whereas the MMT platelets create excellent barrier and thermal shielding properties by forming inorganic lamellae within the P-CNF matrix. These films showed a tensile strength of 304 MPa and a Young's modulus of 15 GPa with 10 wt % clay so that this composite film was mechanically stronger than the previously prepared CNF/clay nanopapers containing the same amount of clay.