Spiers Memorial Lecture: organic, physical & polymer aspects pivotal in lignin valorization.

Discovering Biomass Structural Determinants Defining the Properties of Plant-Derived Renewable Carbon Fiber

Fractionation and characterization of industrial lignins

Due to their polyphenolic structure lignins bear a number of interesting functional properties, such as antioxidant activity. Natural antioxidants are very much looked for in the aim of protection of light or oxygen sensitive goods and are being used in active packaging. Poly(lactide) (PLA)-lignin films were prepared by twin screw extrusion followed by thermo-compression using two different commercial sources of alkali lignins obtained from gramineous plants. A good dispersion of lignin in the matrix was observed. Mechanical properties of the compounded material were merely diminished and oxygen barrier properties slightly enhanced. The chromatographic study of the lignins revealed that the low molecular weight fraction of both lignins increased during the polymer processing. The migration of low molecular weight compounds in an ethanol/water solution simulating fatty foodstuff was performed and the antioxidant activity of the extract was analysed. It was found that the activity increases with increasing severity of the heat treatment because of the generation of free phenolic monomers during processing. These results open an interesting way for application of lignins as an active compound in packaging materials. Lignins do not impair the mechanical and barrier performance of the polymer and the plastics processing even allows for the generation of active substances.

This article provides UV-spectrophotometry data of technical lignin samples in solutions, which were acquired after ambient aging for up to 110 days or looped measurements on fresh solutions. UV-spectrophotometry of lignin is a useful technique, as it can a) quantify the concentration and purity of lignin in a given sample, b) determine the abundance of phenolic hydroxyl groups, and c) yield qualitative information about chemical modification of the lignin macromolecule. In addition, the technique is rapid and easy to use. Still, solutions of lignin are known to be unstable; in particular at high pH or in presence of UV-light. The data in this article may hence serve as guide in the experimental conduct and design, as it shows the reproducibility of UV-spectrophotometry measurements of lignin. Stock solutions of technical lignin were made according to previously published procedure [1]. The solutions in dimethyl sulfoxide (DMSO) were aged in 100 mL volumetric flasks with glass stopper, taking periodic samples for measurements in a Shimadzu UV-1900 UV−vis spectrophotometer. The instrument recorded the spectrum from 500 to 200 nm at 1.0 nm intervals and medium speed, using quartz cuvettes with a pathlength of 1 cm. In addition, looped measurements were conducted on fresh solutions, where the instrument repeated the spectral range of 500 to 200 nm for in total sixteen times. The latter examined solutions of technical lignin in DMSO solvent as well as in 0.2 N NaOH in water.

Fractionation and oxypropylation of corn-stover lignin for the production of biobased rigid polyurethane foam

ABSTRACTLignin readily dissolves in a deep eutectic solvent (DES) composed of ZnCl2/acetamide 1:3 M ratio in concentrations up to 16.7 wt %, and upon addition of water, two fractions were obtained; one composed of lignin with low‐molecular weight that remained dissolved in the DES/water mixture, whereas the other fraction of lignin with higher molecular weight (regenerated lignin, RL) was regenerated by precipitation. Both the RL fraction and the whole solution of lignin in DES were used to replace part of phenol (20 wt %) in the condensation of phenol and formaldehyde to introduce biomass in the resulting resins. The lignin treatment that produced the higher yield of RL consisted of lignin/DES ratio of 1:10 (w/w) stirred for 4 h at 100 °C. By using 13C NMR spectroscopy, a preferential cleavage of the S unit of lignin during DES treatment was identified. The modified phenol‐formaldehyde resin (RLPF) containing the RL exhibited higher bonding strength (1.28 ± 0.16 MPa) and shorter Sunshine gel time (557 s) than PF (587 s), showing that the RL helps to improve the polycondensation process. The resin modified with the whole solution of lignin in DES exhibited the shortest Sunshine gel time due to the effect of zinc(II) accelerating the curing process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48385.

Synergistically program thermal expansional and mechanical performances in 3D metamaterials: Design-Architecture-Performance

The production of lignin fibers has been studied in order to replace the need for petroleum based precursors for carbon fiber production. In addition to its positive environmental effects, it also benefits the economics of the industries which cannot take advantage of carbon fiber properties because of their high price. A large amount of lignin is annually produced as the byproduct of paper and growing cellulosic ethanol industry. Therefore, finding high value applications for this low cost, highly available material is getting more attention. Lignin is a biopolymer making about 15 – 30 % of the plant cell walls and has a high carbon yield upon carbonization. However, its processing is challenging due to its low molecular weight and also variations based on its origin and the method of separation from cellulose. In this study, alkali solutions of organosolv lignin with less than 1 wt/v% of poly (ethylene oxide) and two types of lignin (hardwood and softwood) were electrospun followed by carbonization. Different heating programs for carbonization were tested. The carbonized fibers had a smooth surface with an average diameter of less than 5 µm and the diameter could be controlled by the carbonization process and lignin type. Scanning electron microscopy (SEM) was used to study morphology of the fibers before and after carbonization. Thermal conductivity of a sample with amorphous carbon was 2.31 W/m.K. The electrospun lignin carbon fibers potentially have a large range of application such as in energy storage devices and water or gas purification systems.

Thin nanocomposite films of thermoplastic starch, chitosan and cellulose nanofibers (bacterial cellulose or nanofibrillated cellulose) were prepared for the first time by solvent casting of water based suspensions of the three polysaccharides. The role of the different bioploymers on the final properties (thermal stability, transparency, mechanical performance and antimicrobial activity) of the films was related with their intrinsic features, contents and synergic effects resulting from the establishment of interactions between them. Thermoplastic starch displays an important role on the thermal stability of the films because it is the most stable polysaccharide; however it has a negative impact on the mechanical performance and transparency of the films. The addition of chitosan improves considerably the transparency (up to 50 % transmittance for 50 % of chitosan, in respect to the amount of starch), mechanical performance and antimicrobial properties (at least 25 % of chitosan and no more than 10 % of cellulose nanofibers are required to observe bacteriostatic or bactericidal activity) but decrease their thermal stability. The incorporation of cellulose nanofibers had the strongest positive impact on the mechanical properties of the materials (increments of up to 15 and 30 MPa on the Young′s modulus and Tensile strength, respectively, for films with 20 % of BC or NFC). Nonetheless, the impact in thermal stability and mechanical performance of the films, promoted by the addition of chitosan and cellulose nanofibres, respectively, was higher than the expected considering their percentage contents certainly because of the establishment of strong and complex interactions between the three polysaccharides.

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.

Refining of industrial lignin to produce homogeneous fractions is essential for high-value applications. However, the understanding of key interactions between a variety of solvents with lignin polymer is still uncertain. In this work, single-step fractionation of industrial hardwood kraft lignin (HKL) using organic solvents of different polarities – ethanol, acetone, diethyl ether and hexane – was investigated by combining an experimental and theoretical approach. Experimental results revealed that higher polarity solvents (ethanol and acetone) exhibited higher solubility yield compared to moderate and low polarity solvents. The chemical differences between lignin fractions were proven by pyrolysis gas chromatography mass spectrometry and near infrared spectroscopy. Density functional theory (DFT) results indicated that ethanol presented higher interaction energy followed by acetone, diethyl ether and hexane, which was consistent with experimental findings. Hydrogen bond and non-covalent interaction results from DFT demonstrated that the predominant interaction was found for high polarity of ethanol over other solvents and γ-OH in the lignin model is the key site.

BackgroundCellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H, respectively). Three different lignin fractions were extracted using ethanol, followed by p-dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively).ResultsEach lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weights for the other two lignin fractions were similar. 31P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p-hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β-O-4 linkages with small amounts of β-5 and β–β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.ConclusionsOverall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.

Selection of kraft lignin fractions as a partial substitute for phenol in synthesis of phenolic resins: Structure-property correlation

Improved mechanical performance of biodegradable polyester based on 1,3-butanediol

Lignin concentration and fractionation from ethanol organosolv liquors by ultra- and nanofiltration