Cellulose nanocrystals (CNCs) are gaining interest as a "green" nanomaterial with superior mechanical and chemical properties for high-performance nanocomposite materials; however, there is a lack of accurate material property characterization of individual CNCs. Here, a detailed study of the topography, elastic and adhesive properties of individual wood-derived CNCs is performed using atomic force microscopy (AFM). AFM experiments involving high-resolution dynamic mode imaging and jump-mode measurements were performed on individual CNCs under ambient conditions with 30% relative humidity (RH) and under a N(2) atmosphere with 0.1% RH. A procedure was also developed to calculate the CNC transverse elastic modulus (E(T)) by comparing the experimental force-distance curves measured on the CNCs with 3D finite element calculations of tip indentation on the CNC. The E(T) of an isolated CNC was estimated to be between 18 and 50 GPa at 0.1% RH; however, the associated crystallographic orientation of the CNC could not be determined. CNC properties were reasonably uniform along the entire CNC length, despite variations along the axis of 3-8 nm in CNC height. The range of RH used in this study was found to have a minimal effect on the CNC geometry, confirming the resistance of the cellulose crystals to water penetration. CNC flexibility was also investigated by using the AFM tip as a nanomanipulator.
Abstract:Eucalyptus species are native to Australia but grown extensively worldwide as short rotation hardwoods for a variety of products and as ornamentals. We describe their general importance with specific emphasis on existing and emerging markets as energy products and the potential to maximize their productivity as short rotation woody crops. Using experience in Florida USA and similar locations, we document their current energy applications and assess their productivity as short-term and likely long-term energy and related products.
Cellulose nanofibrils (CNFs) are a class of cellulosic nanomaterials with high aspect ratios that can be extracted from various natural sources. Their highly crystalline structures provide the nanofibrils with excellent mechanical and thermal properties. The main challenges of CNFs in nanocomposite applications are associated with their high hydrophilicity, which makes CNFs incompatible with hydrophobic polymers. In this study, highly transparent and toughened poly(methyl methacrylate) (PMMA) nanocomposite films were prepared using various percentages of CNFs covered with surface carboxylic acid groups (CNF-COOH). The surface groups make the CNFs interfacial interaction with PMMA favorable, which facilitate the homogeneous dispersion of the hydrophilic nanofibrils in the hydrophobic polymer and the formation of a percolated network of nanofibrils. The controlled dispersion results in high transparency of the nanocomposites. Mechanical analysis of the resulting films demonstrated that a low percentage loading of CNF-COOH worked as effective reinforcing agents, yielding more ductile and therefore tougher films than the neat PMMA film. Toughening mechanisms were investigated through coarse-grained simulations, where the results demonstrated that a favorable polymer-nanofibril interface together with percolation of the nanofibrils, both facilitated through hydrogen bonding interactions, contributed to the toughness improvement in these nanocomposites.
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