Commercial birch xylan (CX) and alkali-soluble birch xylan (ASX) were subjected to controlled acetylation and used for film formation in the presence (20% and 40%) or absence of plasticizers (i.e. glycerol, sorbitol and xylitol). Although the content of Klason lignin was similar (1.2-1.4%), the acetylation process was favored by the high-purity CX (97% xylan) over the ASX (89% xylan). On the other hand, the presence of residual pectin heteropolysaccharides rather than xylan in the ASX sample was beneficial for film formation. These heteropolysaccharides seemed to act as natural plasticizers during film formation, allowing the formation of coherent films from ASX, even in the absence of an external plasticizer. The use of plasticizers favored the mechanical properties of films, especially in a dosage of 40%, when plastic behavior was created. Acetylation favored the film formation and slightly improved the mechanical properties of the films, and this improvement was in the same range as that achieved when using 20% plasticizer in non-acetylated ASX.

Technical lignin particles melt under relatively low temperature. This results in the problem in the continuous feeding and fluidization during lignin pyrolysis, which in turn limits its utilization on a large scale. In this study, two most available types of lignin have been used to investigate the lignin melting problem, which are Kraft lignin (KL) from pulping process and hydrolysis lignin (HL) from bio-ethanol production process. Elemental composition, thermal property and thermally decomposed derivatives of each sample are tested by elemental analyzer, TGA, DSC, and Py-GC/MS. Morphology, structure and crystal change before and after heat treatment are tested by microscopy, FTIR and XRD. All results suggest that lignin structure determines its melting properties. Kraft lignin from pulping process contains a less cross-linked structure. It melts under heating. On the other hand, hydrolysis lignin from hydrolysis process contains a highly crossed-linked and condensed structure. It does not melt before decomposition under heat treatment. Modifying lignin structure is suggested for the resolution of technical lignin melting problem.

Efficient sorbents for the removal of cationic dye were prepared from sugarcane bagasse (stalk) and straw (leaves) by oxidative pre-treatment with hydrogen peroxide (H2O2) in acetic acid. The effects of variables, such as concentration of H2O2, temperature and time on the properties of the fiber sorbents obtained were studied according to a 2(3) full-factorial design. For comparison, an oxidative treatment of sugarcane biomass with glacial acetic acid was also used. The yields of the materials obtained and their chemical composition were characterized and compared. Fourier transform infrared spectroscopy, field-emission scanning electron microscopy and benzene vapor adsorption were used to investigate the structural properties and morphology of the initial materials and sorbents. The sorption of methylene blue dye was used to assess the efficiency of dye removal by the sorbents. The pre-treatment conditions significantly affected the sorbent yield, their chemical composition (contents of cellulose, lignin and ash) as well as their sorption properties. The cellulosic sorbent (C-sorbent) from sugarcane bagasse obtained by pre-treatment with H2O2 in acetic acid and the lignocellulosic sorbent (LC-sorbent) from sugarcane straw obtained by pre-treatment with glacial acetic acid, had the highest sorption capacity for the methylene blue dye. For both types of sorbents, the sorption capacity increased with chemical pretreatment as a result of an increase in pore volume.

In recent years, functional polymeric compounds have been widely used to modify the silica surface, which allows one to obtain the corresponding organomineral composites for broad application prospects. In this case, lignin-a cross-linked polyphenolic macromolecule-is of great interest according to its valuable properties and possible surplus as a by-product of pulp and paper industry and various biorefinery processes. Hybrid materials based on kraft softwood lignin and silica were obtained via the electrostatic attraction of oxidized lignin to the aminosilica surface with different porosities, which were prepared by the amination of the commercial silica gel with an average pore diameter of 6 nm, and the silica prepared in the lab with the oxidized kraft lignin and lignin-silica samples with an average pore diameter of 38 nm was investigated by physicochemical methods: two-dimensional nuclear magnetic resonance (NMR), P-31 NMR, Fourier transform infrared spectroscopy, thermogravimetric analysis in nitrogen and air atmosphere, scanning electron microscopy, and adsorption methods. After oxidation, the content of carboxylic groups almost doubled in the oxidized lignin, compared to that in the native one (0.74 mmol/g against 0.44 mmol/g, respectively). The lignin content was deposited onto the surface of aminosilica, depending on the porosity of the silica material and on the content of amino groups on its surface, giving lignin-aminosilica with 20% higher lignin content than the lignin-aminosilica gel. Both types of lignin-silica composites demonstrate a high sorptive capacity toward crystal violet dye. The suggested approach is an easy and low-cost way of synthesis of lignin-silica composites with unique properties. Such composites have a great potential for use as adsorbents in wastewater treatment processes.

This paper investigated the impact of the amounts of lignin and hemicelluloses on cellulose nanofibers (CNFs). Birch and spruce wood were used to prepare holocellulose and cellulose samples by classical methods. To better assess the effect of the chemical composition on the CNF performance and simplify the process for CNF preparation, no surface derivatization method was applied for CNF preparation. Increased amounts of hemicelluloses, especially mannans, improved the defibration process, the stability of the CNFs and the mechanical properties, whereas the residual lignin content had no significant effect on these factors. On the other hand, high lignin content turned spruce nanopapers yellowish and, together with hemicelluloses, reduced the strain-at-break values. Finally, when no surface derivatization was applied to holocellulose and cellulose samples before defibration, the controlled preservation of residual lignin and hemicelluloses on the CNFs indicate to be crucial for the process. This simplified method of CNF preparation presents great potential for forest-based industries as a way to use forestry waste (e.g., branches, stumps, and sawdust) to produce CNFs and, consequently, diversify the product range and reach new markets.

This paper presents the results of an accelerated aging test of biocomposites containing kraft lignin, where the resistance of the materials against humidity and light exposure was investigated. Low molecular weight lignin, modified with methacrylic anhydride (LWL-Met), was copolymerized with two commercial monomers: styrene (St) and methyl methacrylate (MMA). The biocomposites were obtained by a bulk polymerization method using alpha,alpha'-azoiso-bis-butyronitrile (AIBN) as a free radical polymerization initiator. The Shore D hardness of the obtained materials was determined before and after aging test. The changes in the chemical structures of polymers, as the result of aging were analyzed by using the attenuated total reflection Fourier transform infrared (ATR/FT-IR) spectroscopy method. The thermal behavior and stability of the obtained materials were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The surface topography was determined using the optical topography method to evaluate the changes on the surface of synthesized materials resulted from accelerated aging. Application of modified lignin as a biocomponent in the polymerization process and its influence on the properties of the obtained materials before and after the accelerated aging test are discussed.

This work summarizes the impact of solvent fractionation on the chemical structure, antioxidant activity, heating values, and thermal and adsorption properties of industrial hardwood and softwood kraft lignins. The aim of the research was to develop a simple approach for obtaining lignin fractions with tailored properties for applications in certain materials. Four common industrial solvents, namely, ethyl acetate, ethanol, methanol and acetone, in various combinations, were found to be efficient for separating spruce and eucalyptus kraft lignins into fractions with low polydispersities. The ethanol fraction of spruce and the ethyl acetate fraction of eucalyptus afforded the highest yields. Gel-permeation chromatography analysis was used to evaluate the efficiency of the chosen solvent combination for lignin fractionation. The composition and structure of the lignin material was characterized by elemental analysis, analytical pyrolysis (Py-GC/MS/FID) and P-31 NMR spectro-scopy. The thermal properties of the lignin samples were studied using thermogravimetric analysis. Proximate analysis data (ash, volatile components, organic matter and fixed carbon) was obtained through the direct measurement of weight changes in each experimental curve, and the high heating values (in MJ/kg) were calculated according to equations suggested in the literature. The adsorption properties of fractionated kraft lignins were studied using methylene blue dye. The correlations observed between molecular weight, composition and functionality and the thermal, radical scavenging and adsorption properties of the lignin fractions provides useful information for selecting the appropriate solvent combinations for specific applications of lignin raw materials (including their use as antioxidants, biofuels or sorbents in water treatment processes).

Hybrid microspheres of trimethoxyvinylsilane, divinylbenzene and lignin were synthesized by a suspension polymerization method. Commercially available alkali lignin and the methanol fraction of softwood kraft lignin were used as the bio-component of polymeric microspheres. The methanol fraction of lignin had a high content of phenolic groups and low molecular weight which are desirable features for further methacrylation. The physicochemical and electrokinetic properties of the synthesized materials were analyzed in detail. The preliminary modification of the hybrids with lignin had a noticeable positive effect on the stability and electrokinetic properties of the final products compared to those of unmodified microspheres composed of divinylbenzene and trimethoxyvinylsilane (DVB-TMVS). Thermal properties were investigated by differential scanning calorimetry and thermogravimetric analysis, and the morphology was studied using scanning electron microscopy. The microsphere texture was characterized using low-temperature nitrogen adsorption. The microspheres were mesoporous with a specific surface area in the range of 149–305 m2/g. The porosity of the hybrid materials was influenced by the type and modification of the lignin; microspheres with modified lignin in general had more developed porous structures. The applicability of the porous materials obtained as sorbents for the removal of dyes was confirmed in a batch experiment. The mechanism of interactions between dyes and a bio-sorbent containing lignin may involve electrostatic interactions between the positively charged nitrogen atoms of the dye molecule and the dissociated functional groups of the adsorbent, hydrogen bonding and π-π interactions.

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.

This work investigates the impact of lignin origin and structural characteristics, such as molecular weight and functionality, on the properties of corresponding porous biopolymeric microspheres obtained through suspension-emulsion polymerization of lignin with styrene (St) and/or divinylbenzene (DVB). Two types of kraft lignin, which are softwood (Picea abies L.) and hardwood (Eucalyptus grandis), fractionated by common industrial solvents, and related methacrylates, were used in the synthesis. The presence of the appropriate functional groups in the lignins and in the corresponding microspheres were investigated by attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR), while the thermal properties were studied by differential scanning calorimetry (DSC). The texture of the microspheres was characterized using low-temperature nitrogen adsorption. The swelling studies were performed in typical organic solvents and distilled water. The shapes of the microspheres were confirmed with an optical microscope. The introduction of lignin into a St and/or DVB polymeric system made it possible to obtain highly porous functionalized microspheres that increase their sorption potential. Lignin methacrylates created a polymer network with St and DVB, whereas the unmodified lignin acted mainly as an eco-friendly filler in the pores of St-DVB or DVB microspheres. The incorporation of biopolymer into the microspheres could be a promising alternative to a modification of synthetic materials and a better utilization of lignin.