Effect of Oxalic Acid Concentration and Different Mechanical Pre-Treatments on the Production of Cellulose Micro/Nanofibers.

The present work analyzes the effect of process variables and the method of characterization of cellulose micro/nanofibers (CMNFs) obtained by different treatments. A chemical pre-treatment was performed using oxalic acid at 25 wt.% and 50 wt.%. Moreover, for mechanical pre-treatments, a rotary homogenizer or a PFI mill refiner were considered. For the mechanical fibrillation to obtain CMNFs, 5 and 15 passes through a pressurized homogenization were considered. The best results of nanofibrillation yield (76.5%), transmittance (72.1%) and surface charges (71.0 µeq/g CMNF) were obtained using the PFI mill refiner, 50 wt.% oxalic acid and 15 passes. Nevertheless, the highest aspect ratio (length/diameter) determined by Transmission Electron Microscopy (TEM) was found using the PFI mill refiner and 25 wt.% oxalic acid treatment. The aspect ratio was related to the gel point and intrinsic viscosity of CMNF suspensions. The values estimated for gel point agree with those determined by TEM. Moreover, a strong relationship between the intrinsic viscosity [η] of the CMNF dispersions and the corresponding aspect ratio (p) was found (ρ[η] = 0.014 p2.3, R2 = 0.99). Finally, the tensile strength of films obtained from CMNF suspensions was more influenced by the nanofibrillation yield than their aspect ratio.

High strength biobased films prepared from xylan/chitosan polyelectrolyte complexes in the presence of ethanol.

The effect of different ethanol concentrations (0; 3; 9; 12 and 16 wt%) on the degree of ionization of xylan and chitosan, the characteristics of polyelectrolyte complex (PEC) suspensions, and the derived films, were exhaustively analyzed through several analytical techniques. Results indicate that the degree of ionization of both polyelectrolytes was reduced, whereas particle sizes and z-potential values of PEC suspensions were remarkably modified. As ethanol concentration was increased up to 12 wt%, the crystallinity of films decreased. Furthermore, the stress at break increased from 45 to 75 MPa. Wet stress-strain results were promising (up to 5.0 MPa, 55%) for all films. Although water vapor permeability was not modified, the swelling capacity was favorably reduced (12%). Results reveal that, for preparing films, it might not be necessary to remove all the ethanol used for xylan precipitation and purification.

Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper.

Complexes of xylan and synthetic polyelectrolytes. Characterization and adsorption onto high quality unbleached fibres.

In this work, polyelectrolyte complexes (PECs) were formed by adding polyacrylic acid (PAA) or 4-O-methylglucuronoxylan (Xyl) on poly(allylamine hydrochloride) (PAH) solutions, at different ionic strength and neutral pH. Turbidity curves, charge densities of the cationic complexes determined by polyelectrolyte titration method, and z-potential values showed clear differences between both complexes. Stirring favourably reverses the effects of sedimentation of Xyl/PAH complexes, as demonstrated by colloidal stability tests. Adsorption studies on silica surfaces, performed by Quartz Crystal Microbalance with Dissipation (QCM-D) showed that PAA/PAH adsorbed complexes layers were rigid, while the corresponding Xyl/PAH layers were viscoelastic. Despite the different conformations, both complexes were adsorbed as spherical particles, as observed by Atomic Force Microscopy (AFM). Adsorption isotherms performed on fibre suspensions showed that the ionic strength of the liquid medium determines the amount of PEC retained. Finally, it was found that the papermaking properties were significantly increased due to the addition of these PECs.

The deacetylation reaction in Eucalyptus wood: kinetics and effects on the effective diffusion.

The removal of native acetyl groups from hardwood O-acetyl-glucuronoxylan has a strong effect on physical characteristics, accessibility and structure of this polymer. The removal also has effects on the swelling and ion transport capacity of the cell wall of hardwoods. In this work, a kinetic expression for Eucalyptus wood deacetylation is determined. Two liquid mediums are considered: a simple alkaline one and another with a higher sodium concentration. The kinetic expression is a power law for the acetyl content and the concentrations in the liquid medium dependence, and is an Arrhenius type expression for temperature dependence. The kinetic expression can be useful to predict the physical properties of wood since the analysis of deacetylation effects on effective capillarity (ECCSA) shows that the acetyl content is a determining factor of wood ionic transport capacity.