Bio-based nanocellulose has been shown to possess impressive mechanical properties and simplicity for chemical modifications. The chemical properties are largely influenced by the surface area and functionality of the nanoscale materials. However, finding the typical cross-sections of nanocellulose, such as cellulose nanofibers (CNFs), has been a long-standing puzzle, where subtle changes in extraction methods seem to yield different shapes and dimensions. Here, we extracted CNFs from wood with two different oxidation methods and variations in degree of oxidation and high-pressure homogenization. The cross-sections of CNFs were characterized by small-angle X-ray scattering and wide-angle X-ray diffraction in dispersed and freeze-dried states, respectively, where the results were analyzed by assuming that the cross-sectional distribution was quantized with an 18-chain elementary microfibril, the building block of the cell wall. We find that the results agree well with a pseudosquare unit having a size of about 2.4 nm regardless of sample, while the aggregate level strongly depends on the extraction conditions. Furthermore, we find that aggregates have a preferred cohesion of phase boundaries parallel to the (110)-plane of the cellulose fibril, leading to a ribbon shape on average.

Nanostructured materials made through flow-assisted assembly of proteinaceous or polymeric nanosized fibrillar building blocks are promising contenders for a family of new high-performance biocompatible materials in a wide variety of applications. Optimization of these processes relies on improving our knowledge of the physical mechanisms from nano-to macroscale and especially understanding the alignment of elongated nanoparticles in flows. Here, we study the full projected orientation distributions of cellulose nanocrystals (CNC) and nanofibrils (CNF) in confined flow using scanning microbeam SAXS. For CNC, we further compare with a simulated system of dilute Brownian ellipsoids, which agrees well at dilute concentrations. However, increasing CNC concentration to a semi-dilute regime results in locally arranged domains called tactoids, which aid in aligning the CNC at low shear rates, but limit alignment at higher rates. Similarly, shear alignment of CNF at semi-dilute conditions is also limited owing to probable bundle/flock formation of the highly entangled nanofibrils. This work provides a first quantitative comparison of full projected orientation distributions of elongated nanoparticles in confined flow and provides an important stepping stone towards predicting and controlling processes to create nanostructured materials on an industrial scale.

High aspect ratio carboxycellulose nanofibers (NOCNF), having typical length over 1000 nm, width ∼4.6 nm, thickness ∼1.3 nm, and carboxylate content of 0.42 mmol/g, were extracted from jute fibers using a modified nitro-oxidation method. The extracted nanofiber was found to possess crystallinity of 69% (measured by wide-angle X-ray diffraction, WAXD), relatively higher than that of raw jute fibers (crystallinity ∼61%). Gelation of NOCNF in aqueous suspensions was observed due to the high aspect ratio of the fiber even at a relatively low concentration. Rheological studies on the NOCNF suspensions at different concentrations (0.01−1 wt %) revealed the shear-thinning behavior with increasing shear rate. The corresponding viscoelastic moduli (G′ and G′′) results indicated that the NOCNF suspension at concentration between 0.1 and 0.2 wt % possessed a liquid−gel transition. The rheological data near the gelation point could be fitted by the Winter−Chambon model, where the results confirmed the formation of a percolated fibrous network. The flow behavior of the NOCNF suspensions in the chosen concentration range could be further described by the concept of the crowding factor. Nanopaper prepared using these high aspect ratio carboxycellulose nanofibers exhibited good mechanical properties with tensile strength of 108 ± 2 MPa and Young's modulus of 4.1 ± 0.2 GPa.

We present a shear-free flow-focusing mixing experiment to study time-resolved reaction kinetics of nanoscale materials through scanning-SAXS.