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Vat photopolymerization (VP) additive manufacturing involves selectively curing low‐viscosity photopolymers via exposure to ultraviolet light in a layer‐wise fashion. Dispersing filler materials in the photopolymer enables tailored end‐use properties, but also increases the viscosity and the timescale associated with interparticle network structural recovery postshear. These rheological properties influence self‐leveling and recoating of the liquid photopolymer mixture during VP. Herein, viscosity of photopolymer and rigid spherical glass microparticles (filler) is experimentally determined as a function of filler fraction, filler size distribution (mono‐ and polydisperse), shear rate, and temperature, which are important VP process parameters. Employing existing viscosity models for mono‐ and polydisperse polymer mixtures demonstrates that particle–particle interactions and the formation of nonspherical clusters of particles strongly affect the viscosity of both monodisperse and polydisperse mixtures with particle volume fractions > 0.05 due to agglomeration/deagglomeration of clusters at elevated shear rates. Consequently, unmodified viscosity models, which assume uniformly dispersed, rigid, spherical particles, are applicable only for mixtures with particle volume fractions < 0.05. It is shown that modifying model parameters such as the fluidity limit and intrinsic viscosity, which explicitly account for nonspherical clusters of particles, improves agreement between viscosity models and experiments, in particular when using a fractal approach. 

Site-specific modification is a great challenge for polysaccharide scientists. Chemo- and regioselective modification of polysaccharide chains can provide many useful natural-based materials and help us illuminate fundamental structure–property relationships of polysaccharide derivatives. The hemiacetal reducing end of a polysaccharide is in equilibrium with its ring-opened aldehyde form, making it the most uniquely reactive site on the polysaccharide molecule, ideal for regioselective decoration such as imine formation. However, all natural polysaccharides, whether they are branched or not, have only one reducing end per chain, which means that only one aldehyde-reactive substituent can be added. We introduce a new approach to selective functionalization of polysaccharides as an entrée to useful materials, appending multiple reducing ends to each polysaccharide molecule. Herein, we reduce the approach to practice using amide formation. Amine groups on monosaccharides such as glucosamine or galactosamine can react with carboxyl groups of polysaccharides, whether natural uronic acids like alginates, or derivatives with carboxyl-containing substituents such as carboxymethyl cellulose (CMC) or carboxymethyl dextran (CMD). Amide formation is assisted using the coupling agent 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). By linking the C2 amines of monosaccharides to polysaccharides in this way, a new class of polysaccharide derivatives possessing many reducing ends can be obtained. We refer to this class of derivatives as multi-reducing-end polysaccharides (MREPs). This new family of derivatives creates the potential for designing polysaccharide-based materials with many potential applications, including in hydrogels, block copolymers, prodrugs, and as reactive intermediates for other derivatives. 

In automated layup manufacturing processes of fiber-reinforced polymer composites, the quality of the manufactured part is strongly dependent on frictional behavior. Improper control of frictional forces can lead to defect formation. Frictional sliding rheometry tests provide an innovative methodology to accurately characterize the tool-ply friction of unidirectional (UD) prepreg employing unique annular plate geometries. The effect of processing parameters (temperature, velocity, and normal force) on the frictional response of a carbon fiber prepreg was studied. Moreover, utilizing custom designed plate geometries coupled with optically transparent fixtures allowed for in-situ quantification of the prepreg-rigid surface contact area along with simultaneous characterization of the process parameter-dependent frictional mechanisms. Our findings highlight the reduction in frictional forces with increasing temperature, attributed to the increased resin flowability, while increases in sliding rates resulted in a pronounced increase in the frictional forces. The effect of applied load on the frictional characteristics was more complicated due to contributions from both the adhesive and normal forces. Finally, the results were interpreted in light of the contact area measurements performed at different temperatures, normal force, and sliding rate.