Wet spinning of strong cellulosic fibres with incorporation of phase change material capsules stabilized by cellulose nanocrystals.

Incorporating a phase change material (PCM) into fibres allows the fabrication of smart textiles with thermo-regulating properties. Previously, such fibres have been made from thermoplastic polymers, usually petroleum-based and non-biodegradable, or from regenerated cellulose, such as viscose. Herein, strong fibres are developed from aqueous dispersions of nano-cellulose and dispersed microspheres with phase changing characteristics using a wet spinning technique employing a pH shift approach. Good distribution of the microspheres and proper compatibility with the cellulosic matrix was demonstrated by formulating the wax as a Pickering emulsion using cellulose nanocrystals (CNC) as stabilizing particles. The wax was subsequently incorporated into a dispersion of cellulose nanofibrils, the latter being responsible for the mechanical strength of the spun fibres. It was possible to produce fibres highly loaded with the microspheres (40 wt%) with a tenacity of 13 cN tex-1 (135 MPa). The fibres possessed good thermo-regulating features by absorbing and releasing heat without undergoing structural changes, while maintaining the PCM domain sizes intact. Finally, good washing fastness and PCM leak resistance were demonstrated, making the fibres suitable for thermo-regulative applications. Continuous fabrication of bio-based fibres with entrapped PCMs may find applications as reinforcements in composites or hybrid filaments.

Silica-rich regenerated cellulose fibers enabled by delayed dissolution of silica nanoparticles in strong alkali using zinc oxide.

Silica nanoparticles (SNPs) dissolve in alkaline media, which limits their use in certain applications. Here, we report a delayed dissolution of SNPs in strong alkali induced by zinc oxide (ZnO), an additive which also limits gelation of alkaline cellulose solutions. This allows incorporating high solid content of silica (30 wt%) in cellulose solutions with retention of their predominant viscous behavior long enough (ca. 180 min) to enable fiber wet spinning. We show that without addition of ZnO, silica dissolves completely, resulting in strong gelation of cellulose solutions that become unsuitable for wet spinning. With an increase of silica concentration, gelation of the solutions occurs faster. Employing ZnO, silica-rich regenerated cellulose fibers were successfully spun, possessing uniform cross sections and smooth surface structure without defects. These findings are useful in advancing the development of functional man-made cellulose fibers with incorporated silica, e.g., fibers with flame retardant or self-cleaning properties.

Nanomaterials for Combined Stabilisation and Deacidification of Cellulosic Materials-The Case of Iron-Tannate Dyed Cotton.

The conservation of textiles is a challenge due to the often fast degradation that results from the acidity combined with a complex structure that requires remediation actions to be conducted at several length scales. Nanomaterials have lately been used for various purposes in the conservation of cultural heritage. The advantage with these materials is their high efficiency combined with a great control. Here, we provide an overview of the latest developments in terms of nanomaterials-based alternatives, namely inorganic nanoparticles and nanocellulose, to conventional methods for the strengthening and deacidification of cellulose-based materials. Then, using the case of iron-tannate dyed cotton, we show that conservation can only be addressed if the mechanical strengthening is preceded by a deacidification step. We used CaCO3 nanoparticles to neutralize the acidity, while the stabilisation was addressed by a combination of nanocellulose, and silica nanoparticles, to truly tackle the complexity of the hierarchical nature of cotton textiles. Silica nanoparticles enabled strengthening at the fibre scale by covering the fibre surface, while the nanocellulose acted at bigger length scales. The evaluation of the applied treatments, before and after an accelerated ageing, was assessed by tensile testing, the fibre structure by SEM and the apparent colour changes by colourimetric measurements.

Evaluation of the Adhesion and Performance of Natural Consolidants for Cotton Canvas Conservation.

Recent developments in paper and canvas conservation have seen the introduction of nanocellulose (NC) as a compatible treatment for the consolidation of historical cellulosic artifacts and manuscripts. However, as part of the assessment of these new materials for canvas consolidation, the adhesion of the consolidation treatment (which takes place between the applied material and the substrate) has not yet been evaluated, and as a result, it is poorly understood by both the scientific and conservation communities. After evaluating the potential of NC treatments for the consolidation of cotton painting canvas, we investigate a route to promote the interaction between the existing canvas and the nanocellulose treatment, which is in our case made of cellulose nanofibrils (CNF). This was carried out by introducing a cationic polymer, polyamidoamine-epichlorohydrin (PAAE), as an intermediate layer between the canvas and the CNF. The morphological, chemical, and mechanical evaluation of the canvas samples at different relative humidity (RH) levels demonstrated how the adhesion of the added PAAE layer is a dominant factor in the consolidation process. Improvement in the coating of canvas single fibers by the CNF, higher adhesion energy between the canvas fibers and the CNF treatment, and finally overall stronger canvas reinforcement were observed following the introduction of PAAE. However, an increase in mechanical response to moisture sorption and desorption was also observed for the PAAE-treated canvases. Overall, this study shows the complexity of such systems and, as such, the relevance of using a multiscale approach for their assessment.

On the potential of using nanocellulose for consolidation of painting canvases.

Nanocellulose has been recently proposed as a novel consolidant for historical papers. Its use for painting canvas consolidation, however, remains unexplored. Here, we show for the first time how different nanocelluloses, namely mechanically isolated cellulose nanofibrils (CNF), carboxymethylated cellulose nanofibrils (CCNF) and cellulose nanocrystals (CNC), act as a bio-based alternative to synthetic resins and other conventional canvas consolidants. Importantly, we demonstrate that compared to some traditional consolidants, all tested nanocelluloses provided reinforcement in the adequate elongation regime. CCNF showed the best consolidation per added weight; however, it had to be handled at very low solids content compared to other nanocelluloses, exposing canvases to larger water volumes. CNC reinforced the least per added weight but could be used in more concentrated suspensions, giving the strongest consolidation after an equivalent number of coatings. CNF performed between CNC and CCNF. All nanocelluloses showed better consolidation than lining with synthetic adhesive (Beva 371) and linen canvas in the elongation region of interest.

Wet Spinning of Flame-Retardant Cellulosic Fibers Supported by Interfacial Complexation of Cellulose Nanofibrils with Silica Nanoparticles.

The inherent flammability of cellulosic fibers limits their use in some advanced applications. This work demonstrates for the first time the production of flame-retardant macroscopic fibers from wood-derived cellulose nanofibrils (CNF) and silica nanoparticles (SNP). The fibers are made by extrusion of aqueous suspensions of anionic CNF into a coagulation bath of cationic SNP at an acidic pH. As a result, the fibers with a CNF core and a SNP thin shell are produced through interfacial complexation. Silica-modified nanocellulose fibers with a diameter of ca. 15 µm, a titer of ca. 3 dtex and a tenacity of ca. 13 cN tex-1 are shown. The flame retardancy of the fibers is demonstrated, which is attributed to the capacity of SNP to promote char forming and heat insulation on the fiber surface.

Current Progress in Rheology of Cellulose Nanofibril Suspensions.

Cellulose nanofibrils (CNFs) are produced and commonly used in the form of aqueous suspensions or gels. A number of studies have focused lately on rheological properties of CNF suspensions, which gives insight into properties of such materials and can reflect their behavior during handling. This Review summarizes the recent progress in rheological studies on CNF aqueous suspensions using rotational rheometry. Here, we discuss linear viscoelastic properties, i.e., frequency-dependent storage and loss moduli; shear flow behavior, i.e., apparent viscosity and shear stress as a function of shear rate; local flow characteristics, etc. In this Review, we point out that the rheological behavior of at least two types of CNF suspensions should be distinguished: (i) ones produced using mechanical fibrillation with or without enzymatic pretreatment (no surface chemical modification), which possess highly flocculated structure, and (ii) ones produced involving chemical modification pretreatments, e.g., carboxylation, carboxymethylation, quaternization, or sulfonation, which possess better colloidal stability and do not evidently flocculate.

Effect of the oxidation treatment on the production of cellulose nanofiber suspensions from Posidonia oceanica: The rheological aspect.

Different grades of cellulose nanofibrils (CNF) were prepared from Posidonia oceanica balls and leaves (POB and POL). Pretreatment using 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation was performed to facilitate the fibrillation during ultrafine friction grinding process. The ensuing CNF batches were compared in terms of morphology and degree of fibrillation. The rheological properties of the produced CNF suspensions were also analyzed for varying doses of sodium hypochlorite used during the TEMPO- mediated oxidation procedure. The stronger fibrous network structures were formed when increasing the oxidant concentration, which was confirmed by the increase of the storage moduli value. P. oceanica balls were found to undergo stronger fibrillation and, consequently, to form stronger networks, compared to P. oceanica leaves, when using equivalent concentration of the oxidizing agent.

Rheological properties of micro-/nanofibrillated cellulose suspensions: wall-slip and shear banding phenomena.

The rheological properties of enzymatically hydrolyzed and TEMPO-oxidized microfibrillated/nanofibrillated cellulose (MFC/NFC) aqueous suspensions were investigated in oscillation and steady-flow modes and were compared with the morphology of the studied materials. The flow instabilities, which introduce an error in the rheological measurements, were discovered during flow measurements. A wall-slip (interfacial slippage on the edge of geometry tools and suspension) was detected at low shear rates for two types of NFC suspensions while applying cone-plate geometry. A roughening of the tool surfaces was performed to overcome the aforementioned problem. Applying to TEMPO-oxidized NFC, a stronger suspension response was detected at low shear rates with higher values of measured shear stress. However, a shear banding (localization of shear within a sample volume) became more pronounced. The use of serrated tools for enzymatically hydrolyzed NFC produced lower shear stress at the moderate shear rates, which was influenced by water release from the suspension.