Hydrogels comprising cellulose nanofibrils (CNF) were used in the synthesis of continuous filaments via wet-spinning. Hydrogel viscosity and spinnability, as well as orientation and strength of the spun filaments, were found to be strongly affected by the osmotic pressure as determined by CNF surface charge and solid fraction in the spinning dope. The tensile strength, Young’s modulus and degree of orientation (wide-angle X-ray scattering, WAXS) of filaments produced without drawing were 297 MPa, 21 GPa and 83%, respectively, which are remarkable values. A thorough investigation of the interactions with water using dynamic vapour sorption (DVS) experiments revealed the role of sorption sites in the stability of the filaments in wet conditions. DVS analysis during cycles of relative humidity (RH) between 0 and 95% revealed major differences in water uptake by the filaments spun from hydrogels of different charge density (CNF and TEMPO-oxidised CNF). It is concluded that the mechanical performance of filaments in the presence of water deteriorates drastically by the same factors that facilitate fibril alignment and, consequently, enhance dry strength. For the most oriented filaments, the maximum water vapour sorption at 95% RH was 39% based on dry weight.

Nanocelluloses are bio-based nanoparticles of interest as stabilizers for oil-in-water (o/w) Pickering emulsions. In this work, the surface chemistry of nanocelluloses of different length, nanofibrillated cellulose (NFC, long) and cellulose nanocrystals (CNC, short), was successfully tailored by chemical modification with lauroyl chloride (C12). The resulting nanofibers were less hydrophilic than the original and able to stabilize water-in-oil (w/o) emulsions. The combination of the two types of nanocelluloses (C12-modified and native) led to new surfactant-free oil-in-water-in-oil (o/w/o) double emulsions stabilized by nanocellulose at both interfaces. Characterization was performed with respect to droplet size distribution, droplet stability over time, and stability after centrifugation. Nanocellulose-based Pickering emulsions can be designed with a substantial degree of control, as demonstrated by the stability of the chemically tailored NFC double emulsions. Furthermore, it was demonstrated that increased nanofiber length leads to increased stability.

This survey constitutes the first part of a comprehensive review, whose purpose is to provide a reasoned perspective in the field related to the preparation of new polysaccharide-based hydrophobic materials by scrutinizing the actual state of its art. This part of the review is entirely dedicated to cellulose, by far the most probed natural substrate, where publications dealing with both chemical and physical treatments aimed at inducing a substantial increase in the hydrophobic character of the surface are critically examined. Furthermore, this initiative constitutes an attempt to emphasize the relevance of this topic within the broader context of the elaboration of novel materials based on renewable resources as a viable alternative to their fossil-based counterparts.

This survey constitutes the second part of a comprehensive review, whose purpose is to provide a reasoned perspective on the field related to the preparation of new polysaccharide-based hydrophobic materials by scrutinizing the actual state of its art. After dealing with the major topic of cellulose hydrophobization in the first part, attention is now turned to the other important members of the polysaccharide families, namely hemicelluloses, chitin/chitosan, starch, pectin and alginates. Publications dealing with both chemical and physical treatments aimed at inducing a substantial increase in the hydrophobic character of their surface are critically examined within the broader context of the elaboration of novel materials based on renewable resources as a viable alternative to their fossil-based counterparts.

A continuous and scalable method for the wet spinning of cellulose nanofibrils (CNFs) is introduced in a core/shell configuration. Control on the interfacial interactions was possible by the choice of the shell material and coagulant, as demonstrated here with guar gum (GG) and cellulose acetate (CA). Upon coagulation in acetone, ethanol, or water, GG and CA formed supporting polymer shells that interacted to different degrees with the CNF core. Coagulation rate was shown to markedly influence the CNF orientation in the filament and, as a result, its mechanical strength. The fastest coagulation noted for the CNF/GG core/shell system in acetone led to an orientation index of ∼0.55 (Herman’s orientation parameter of 0.40), Young’s modulus of ∼2.1 GPa, a tensile strength of ∼70 MPa, and a tenacity of ∼8 cN/tex. The system that underwent the slowest coagulation rate (CNF/GG in ethanol) displayed a limited CNF orientation but achieved an intermediate level of mechanical resistance, owing to the strong core/shell interfacial affinity. By using CA as the supporting shell, it was possible to spin CNF into filaments with high water absorption capacity (43 g water/g dry filament). This was explained by the fact that water (used as the coagulant for CA) limited the densification of the CNF core structure, yielding filaments with high accessible area and pore density.