Mikael E. Lindstrom

In our previous study, we demonstrated that Eucalyptus dunnii samples containing high calcium content show inferior pulping properties concerning delignification and polysaccharide degradation. This led us to investigate alternative methods for improving the pulping process of these samples. In the present work, we evaluated the effects of incorporating black and green liquors into the Eucalyptus dunnii chips before kraft pulping, aiming to enhance the pulping process and overcome the negative impact of high calcium content. The addition of both black and green liquors resulted in specific enhancements, with the green liquor having a more significant impact on the pulping process. Even wood samples with the highest calcium content demonstrated satisfactory pulping results when treated with green liquor. Delignification occurred more rapidly, and selectivity was higher for samples pre-treated with green liquor before kraft pulping. Moreover, calcium tended to follow the fiber under these conditions rather than being released into the black liquor, which may contribute to the improved pulping performance. Subsequent bleaching tests revealed that the bleachability of green liquor-treated pulp was nearly identical to that of a control pulp, while maintaining a higher viscosity. This suggests that incorporating green liquor into the pre-treatment process not only improves the pulping performance of Eucalyptus dunnii samples with high calcium content but also maintains desirable bleachability characteristics. To better understand the underlying mechanisms of these findings, we discuss the potential chemical explanations behind the observed improvements.

Eucalyptus dunnii is cultivated in Uruguay for kraft pulping purposes. However, depending on the growth site, the kraft pulping properties of the wood vary highly, and in some cases, pulping is difficult. Different batches of wood were chemically characterized and the only significant difference related to the pulping properties was the calcium content. The calcium appears to at least partly be present in the form of crystals in the lumen. Kraft pulping experiments on wood with different calcium contents indicated that high calcium led to slower delignification, and higher yield losses. Hexeneuronic acid formation was not significantly affected. Possible mechanistic explanations for these effects are discussed.

Nanocellulose membranes based on tunicate-derived cellulose nanofibers, starch, and ~5% wood-derived lignin were investigated using three different types of lignin. The addition of lignin into cellulose membranes increased the specific surface area (from 5 to ~50 m²/g), however the fine porous geometry of the nanocellulose with characteristic pores below 10 nm in diameter remained similar for all membranes. The permeation of H₂, CO₂, N₂, and O₂ through the membranes was investigated and a characteristic Knudsen diffusion through the membranes was observed at a rate proportional to the inverse of their molecular sizes. Permeability values, however, varied significantly between samples containing different lignins, ranging from several to thousands of barrers (10⁻¹⁰ cm³ (STP) cm cm⁻² s⁻¹ cmHg⁻¹cm), and were related to the observed morphology and lignin distribution inside the membranes. Additionally, the addition of ~5% lignin resulted in a significant increase in tensile strength from 3 GPa to ~6–7 GPa, but did not change thermal properties (glass transition or thermal stability). Overall, the combination of plant-derived lignin as a filler or binder in cellulose–starch composites with a sea-animal derived nanocellulose presents an interesting new approach for the fabrication of membranes from abundant bio-derived materials. Future studies should focus on the optimization of these types of membranes for the selective and fast transport of gases needed for a variety of industrial separation processes.

Lignin fractions having different molecular weights and varied chemical structures isolated from kraft lignins of both softwood and hardwood via a sequential solvent fractionation technique were incorporated into a tunicate cellulose nanofibers (CNF)—starch mixture to prepare 100% bio-based composite films. The aim was to investigate the impact of lignin structural diversity on film performance. It was confirmed that lignin’s distribution in the films was dependent on the polarity of solvents used for fractionation (acetone > methanol > ethanol > ethyl acetate) and influenced the optical properties of the films. The –OH group content and molecular weight of lignin were positively related to film density. In general, the addition of lignin fractions led to decrease in thermal stability and increase in Young’s modulus of the composite films. The modulus of the films was found to decrease as the molecular weight of lignin increased, and a higher amount of carboxyl and phenolic –OH groups in the lignin fraction resulted in films with higher stiffness. The thermal analysis showed higher char content formation for lignin-containing films in a nitrogen atmosphere with increased molecular weight. In an oxygen atmosphere, the phenol content, saturated side chains and short chain structures of lignin had impacts on the maximum decomposition temperature of the films, confirming the relationship between the chemical structure of lignin and thermo-oxidative stability of the corresponding film. This study addresses the importance of lignin diversities on composite film performance, which could be helpful for tailoring lignin’s applications in bio-based materials based on their specific characteristics.

The development of advanced hybrid materials based on polymers from biorenewable sources and mineral nanoparticles is currently of high importance. In this paper, we applied softwood kraft lignins for the synthesis of lignin/SiO₂ nanostructured composites. We described the peculiarities of composites formation in the sol-gel process through the incorporation of the lignin into a silica network during the hydrolysis of tetraethoxysilane (TEOS). The initial activation of lignins was achieved by means of a Mannich reaction with 3-aminopropyltriethoxysilane (APTES). In the study, we present a detailed investigation of the physicochemical characteristics of initial kraft lignins and modified lignins on each step of the synthesis. Thus, 2D-NMR, ³¹P-NMR, size-exclusion chromatography (SEC) and dynamic light scattering (DLS) were applied to analyze the characteristics of pristine lignins and lignins in dioxan:water solutions. X-Ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) were used to confirm the formation of the lignin–silica network and characterize the surface and bulk structures of the obtained hybrids. Termogravimetric analysis (TGA) in nitrogen and air atmosphere were applied to a detailed investigation of the thermal properties of pristine lignins and lignins on each step of modification. SEM confirmed the nanostructure of the obtained composites. As was demonstrated, the activation of lignin is crucial for the sol-gel formation of a silica network in order to create novel hybrid materials from lignins and alkoxysilanes (e.g., TEOS). It was concluded that the structure of the lignin had an impact on its reactivity during the activation reaction, and consequently affected the properties of the final hybrid materials.

To investigate the dispersibility of dried cellulose nanofibers (CNFs), various additions (glycerol, octanol, glycol, and sodium perchlorate) were added to CNFs prior to drying. Glycerol was the only species to show any significant effect on re-dispersibility. The sedimentation was slower, and the transmittance of the solution was comparable to that of its undried counterpart. Increasing the amount of glycerol showed a clear trend with regard to dispersibility. The mechanical properties of films were maintained for samples that were dried and redispersed in the presence of glycerol.

In this paper, we explore xyloglucan adsorption to cellulose nanofibers as a method for the evaluation of their quality (i. e., the degree of disintegration) and the accessible surface area in the wet state and at low ionic strength. This method was shown to be capable of estimating the surface areas of 14 different cellulose nanofiber qualities from both hardwood and softwood with different pretreatments, including enzymatic hydrolysis using a monocomponent endoglucanase, TEMPO-mediated oxidation, and carboxymethylation. The cellulose surface measured using this method showed a correlation with the degree of disintegration expressed as transmittance for different concentrations of xyloglucan.

The hemicellulose xyloglucan can be utilized to measure exposed cellulose surfaces for pulp fibers. This was shown by correlating a refining series with the adsorbed amount of xyloglucan, and by swelling cellulose fibers to various degrees by increasing the charge density. The method is specific to cellulose and could be used to quantify refining or to determine hornification.