A new family of materials comprised of cellulose, cellulose nanomaterials (CNMs), having properties and functionalities distinct from molecular cellulose and wood pulp, is being developed for applications that were once thought impossible for cellulosic materials. Commercialization, paralleled by research in this field, is fueled by the unique combination of characteristics, such as high on-axis stiffness, sustainability, scalability, and mechanical reinforcement of a wide variety of materials, leading to their utility across a broad spectrum of high-performance material applications. However, with this exponential growth in interest/activity, the development of measurement protocols necessary for consistent, reliable and accurate materials characterization has been outpaced. These protocols, developed in the broader research community, are critical for the advancement in understanding, process optimization, and utilization of CNMs in materials development. This review establishes detailed best practices, methods and techniques for characterizing CNM particle morphology, surface chemistry, surface charge, purity, crystallinity, rheological properties, mechanical properties, and toxicity for two distinct forms of CNMs: cellulose nanocrystals and cellulose nanofibrils.
of nanomaterials from green, low-cost, abundant, renewable, and biodegradable natural resources. One such attractive bioresource is cellulose, the most abundant biopolymer on earth, which is widely present in various forms of renewable biomass, such as trees, plants, tunicates, and bacteria.Structurally, cellulose is a linear, high molecular weight polysaccharide with repeating glucose units linked by 1-4 glycosidic bonds. Owing to the presence of hydroxyl groups, those linear chains of glucose units link together through van der Waals forces and intermolecular hydrogen bonding to form elementary fibrils, which are further packed into larger aggregates known as microfibrils. [3] Cellulose fibrils consist of disordered (amorphous) regions and highly ordered (crystalline) regions. In the crystalline regions, cellulose chains are closely packed together in highly ordered fashion (parallel to the direction of fibril length), dictated by the intricate intraand intermolecular hydrogen bonding; whereas in the amorphous regions, cellulose chain stacking is less ordered and not as closely packed. Therefore, the amorphous regions are more vulnerable to both physical disintegration and chemical hydrolysis in comparison with crystalline regions. When cellulose is prepared in nano-scale fibrillar or crystalline forms, it is broadly referred to as cellulose nanomaterials (CNMs).The isolation, characterization, modification, and application of CNMs are currently receiving much attention. Understanding Cellulose nanomaterials (CNMs), mainly including nanofibrillated cellulose (NFC) and cellulose nanocrystals (CNCs), have attained enormous interest due to their sustainability, biodegradability, biocompatibility, nanoscale dimensions, large surface area, facile modification of surface chemistry, as well as unique optical, mechanical, and rheological performance. One of the most fascinating properties of CNMs is their aqueous suspension rheology, i.e., CNMs helping create viscous suspensions with the formation of percolation networks and chemical interactions (e.g., van der Waals forces, hydrogen bonding, electrostatic attraction/repulsion, and hydrophobic attraction). Under continuous shearing, CNMs in an aqueous suspension can align along the flow direction, producing shear-thinning behavior. At rest, CNM suspensions regain some of their initial structure immediately, allowing rapid recovery of rheological properties. These unique flow features enable CNMs to serve as rheological modifiers in a wide range of fluid-based applications. Herein, the dependence of the rheology of CNM suspensions on test protocols, CNM inherent properties, suspension environments, and postprocessing is systematically described. A critical overview of the recent progress on fluid applications of CNMs as rheology modifiers in some emerging industrial sectors is presented as well. Future perspectives in the field are outlined to guide further research and development in using CNMs as the next generation rheological modifiers.
Recent advances in the field of additive manufacturing (AM) or 3D printing, have garnered serious interest for its potential to substitute time-consuming and costly subtractive and formative manufacturing techniques. Material extrusion (MatEx), employing filament and pelletbased feedstocks, is an AM technique for fabricating three-dimensional objects dictated by a computer-aided design (CAD) file in a layer-by-layer manner. Being inherently a "melt-and-form" technique, the physics of MatEx is strongly dependent on the melt flow behavior of the polymers and hence on their rheology. The focus of this review article is to analyze the current progress in rheological characterizations of filament and pellet-based polymeric feedstocks for application in MatEx. The importance of shear and temperature-dependent viscosities in relation to consistent extrusion through the print nozzle and in the standoff region between nozzle and bed will be highlighted. The importance of shear and/or extensional viscosities and extent of die swell (upon exit from the nozzle) experienced by the polymers under processing parameters relevant to MatEx will be investigated. Postextrusion from the nozzle, the rheological characteristics of the viscous polymer melt as it cools once deposited on the print bed governs the degree of interlayer welding, that impacts the mechanical performance of the printed parts. Controlling and monitoring rheological properties such as zero-shear viscosities and shear moduli of the melt is of significant importance in this region in order to ensure proper mechanical robustness and shape integrity of the deposited layers. Both experimental and theoretical approaches based on polymer chain reptation mechanisms will be reviewed in detail and suggestions to address the existing limitations associated with the process will be provided. Fundamental understanding of the correlation between the classical theories and current understanding based on recent experimentation and analysis is expected to assist the design and development of the next generation of polymer feedstocks and machine designs for MatEx-based AM.
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