ZnO nanorods (length 30–150 nm) were synthesized in di(ethylene glycol) using Zn(CH3COO)2 as a precursor and para‐toluene sulphonic acid, p‐TSA, as an end‐capping agent. Increasing the concentration of p‐TSA above 0.1 M causes the reduction of the ZnO length. Nanocomposites with poly(methyl methacrylate) were prepared using unmodified nanorods. They enhanced the UV absorption of nanocomposites (~98%) at low ZnO concentrations (0.05–0.1 wt.%), while visible light transparency was high. At concentrations of 1 wt.% and above, nanorods enhanced the thermal stability of nanocomposites. At low concentrations (0.05–0.1 wt.%), they increased the storage modulus of material and shifted Tg towards higher temperatures as shown by dynamic mechanical analysis, DMA, while at higher concentrations (1.0 wt.%) this effect was deteriorated. DMA also showed that spherical ZnO particles have a more pronounced effect on the storage modulus and Tg than nanorods.
Cellulose is the most abundant natural polymer and deserves the special attention of the scientific community because it represents a sustainable source of carbon and plays an important role as a sustainable energent for replacing crude oil, coal, and natural gas in the future. Intense research and studies over the past few decades on cellulose structures have mainly focused on cellulose as a biomass for exploitation as an alternative energent or as a reinforcing material in polymer matrices. However, studies on cellulose structures have revealed more diverse potential applications by exploiting the functionalities of cellulose such as biomedical materials, biomimetic optical materials, bio-inspired mechanically adaptive materials, selective nanostructured membranes, and as a growth template for inorganic nanostructures. This article comprehensively reviews the potential of cellulose structures as a support, biotemplate, and growing vector in the formation of various complex hybrid hierarchical inorganic nanostructures with a wide scope of applications. We focus on the preparation of inorganic nanostructures by exploiting the unique properties and performances of cellulose structures. The advantages, physicochemical properties, and chemical modifications of the cellulose structures are comparatively discussed from the aspect of materials development and processing. Finally, the perspective and potential applications of cellulose-based bioinspired hierarchical functional nanomaterials in the future are outlined.
Cellulose nanocrystals (CNCs) were surface modified by esterification in tetrahydrofuran (THF) at 25 °C using different catalysts and anhydrides bearing different alkyl side chain lengths. Unmodified and acetic anhydride (AcAnh)-modified CNCs were studied as potential nanofillers for linear low-density poly(ethylene) (LLDPE). Nanocomposites were prepared by melt processing. Determination of the size and size distribution of CNCs in the nanocomposites by SEM revealed an enhanced compatibility of the AcAnh-modified CNCs with the LLDPE matrix, since the average size of the aggregates of the modified CNCs (0.5–5 μm) was smaller compared to that of the unmodified CNCs (2–20 μm). Tensile test experiments revealed an increase in the nanocomposites’ stiffness and strain at break—by 20% and up to 90%, respectively—at the CNC concentration of 5 wt %, which is close to the critical percolation concentration. Since the CNC nanofiller simultaneously reduced LLDPE crystallinity, the reinforcement effect of CNCs was hampered. Therefore, the molding temperature was increased to 120 °C, and, in this way, the greatest increase of the Young’s modulus was achieved (by ~45%). Despite the enhanced compatibility of the AcAnh-modified CNCs with the LLDPE matrix, no additional effect on the mechanical properties of the nanocomposites was observed in comparison to the unmodified CNC.