Nanostructural Effects in High Cellulose Content Thermoplastic Nanocomposites with a Covalently Grafted Cellulose–Poly(methyl methacrylate) Interface

A critical aspect in materials design of polymer nanocomposites is the nature of the nanoparticle/polymer interface. The present study investigates the effect of manipulation of the interface between cellulose nanofibrils (CNF) and poly­(methyl methacrylate) (PMMA) on the optical, thermal, and mechanical properties of the corresponding nanocomposites. The CNF/PMMA interface is altered with a minimum of changes in material composition so that interface effects can be analyzed. The hydroxyl-rich surface of CNF fibrils is exploited to modify the CNF surface via an epoxide-hydroxyl reaction. CNF/PMMA nanocomposites are then prepared with high CNF content (∼38 wt %) using an approach where a porous CNF mat is impregnated with monomer or polymer. The nanocomposite interface is controlled by either providing PMMA grafts from the modified CNF surface or by solvent-assisted diffusion of PMMA into a CNF network (native and modified). The high content of CNF fibrils of ∼6 nm diameter leads to a strong interface and polymer matrix distribution effects. Moisture uptake and mechanical properties are measured at different relative humidity conditions. The nanocomposites with PMMA molecules grafted to cellulose exhibited much higher optical transparency, thermal stability, and hygro-mechanical properties than the control samples. The present modification and preparation strategies are versatile and may be used for cellulose nanocomposites of other compositions, architectures, properties, and functionalities