Volume 76, Issue 3

The purpose of this study was to examine how the type of solvent among aqueous 1,4-dioxane, tetrahydrofuran, ethanol, iso -propyl alcohol, or ethylene glycol and its content (mol%) affect the formation rate of benzyl cation intermediate (BC) in the acidolysis of lignin, using a simple model compound, 1,2-dimethoxy-4-methoxymethylbenzene. Because the BC forms from the model compound via two steps, i.e. , protonation of the benzyl methoxymethyl group as the pre-equilibrium step and liberation of the methanol as the rate-determining step, the observed variation of the formation rate with type of solvent and solvent content originates from the effects on both steps undistinguishably. The formation rate of BC decreased with increasing mol% of any of the organic solvents for a range of relatively low mol%, but increased with it for relatively high mol%. The formation rate varied more in the ether than in the alcohol systems. These results seem to be regulated by the effect of changing the mol% on the pre-equilibrium step, i . e ., on the proton activity, rather than on the rate-determining step. Two reaction products, 4-alkoxymethyl-1,2-dimethoxybenzene and 4-hydroxymethyl-1,2-dimethoxybenzene, exclusively formed in the aqueous alcohol systems. The former compound was confirmed to be thermodynamically more stable and kinetically the more favorable product.

Susceptibility of wood to UV degradation decreases the service life of wood products outdoors. Organic UV absorbers (UVAs) and hindered amine light stabilizers (HALSs), as well as inorganic UVAs, are added to coatings to improve the UV stability of coated-wood products. Although about 85% of UV radiation is absorbed by lignin in the wood, it is unclear which UV stabilizers can minimize lignin degradation. In this study, the photodegradation of softwood organosolv lignin was monitored over 35 days of UV exposure. Changes in lignin properties were assessed using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and phosphorus-31 nuclear magnetic resonance spectroscopy ( 31 P NMR). It was found that the aromatic rings of lignin underwent significant degradation, resulting in increased glass transition temperature and molecular weight of lignin. Subsequently, 18 different additives were mixed with lignin and exposed to UV irradiation. The analysis of samples before and after UV exposure with FTIR revealed that inorganic UVAs (cerium oxide and zinc oxide) and a mixture of organic UVAs and HALSs (T-479/T-292, T-5248, and T-5333) were the most effective additives in reducing lignin degradation. This study can help coating scientists to formulate more durable transparent exterior wood coatings.

Wood-water interactions affect durability and performance of wood products, such as dimensional stability and biodegradation. To upgrade wood, a combined modification via hemicellulose extraction and furfurylation was proposed to inhibit wood-water interactions. More intense hemicellulose extraction caused larger voids and led to higher pore volume. The increment of porosity resulted in more uniform distribution of polymerized furfural resin in cells, as indicated by scanning electron microscopic and confocal laser scanning microscopic observations. The combined modification greatly reduced surface wettability with an increase of water contact angle (CA) of over 134% at 100 s. With hemicellulose extraction, polymerized furfural resin partially occupied the accommodation initially for water molecules and reduced accessible sorption sites, causing water absorption (WA) of wood to decrease by over 30% after soaking in water for 768 h. Dynamic moisture sorption was weakened after combined modification, and the moderate hemicellulose extraction combined with furfurylation reduced the moisture content by over 50% due to incorporative changes of chemical sorption sites and physical porosity. The results confirmed the efficiency of the combined modification in inhibiting wood-water interactions and indicated the importance to accurately control hemicellulose content during modification. This study could provide useful information for sustainably enhancing wood performance and upgrading low-quality wood.

Plantation-grown poplar ( Populus cathayana ) is regarded as a source of low-quality wood, with poor dimensional stability and low decay resistance. In this study, poplar wood was impregnated with sodium montmorillonite (Na-MMT) or organo-montmorillonite (O-MMT), furfuryl alcohol (FA, at concentrations of 15%, 30% and 50%), separately or in their combinations to prepare clay treated, furfurylated, and clay-reinforced furfurylated wood, respectively. The two-step method by introducing Na-MMT first and then FA and organic modifier was feasible to achieve a reasonable penetration. These components could entirely enter the wood cell lumen or partly enter the wood cell wall, and thus initiate a series of reactions. Compared with Na-MMT reinforced furfurylated wood (M-F), the O-MMT reinforced furfurylated wood (O-F) exhibited better dimensional stability (ASE up to 71%) and decay resistance (3.2% mass loss). Moreover, O-MMT played a predominant role in decay resistance of O-MMT reinforced furfurylated wood. Even at low O-MMT loadings, the modified wood had a significant inhibitory effect on the white-rot decay fungus Trametes versicolor . Based on an overall evaluation, O-MMT reinforced furfurylated wood seemed to provide an optimal choice for both moist or wet conditions.

The improvement of durability and dimensional stability of wood properties via modification of the microstructure and wood–water interaction has been widely utilised. This study investigated polyester treatments, a possible alternative, using environmentally friendly chemicals such as malic acid to improve the beech wood ( Fagus sylvatica ) properties. The modified properties have been studied with four treatments using malic acid, glycerol, butanediol and succinic anhydride, mixing polycarboxylic acids and polyols. Results showed that the anti-swelling-efficiency (ASE) improved up to 70%, and the bulking coefficient improved around 23%, exhibiting an efficient penetration within the cell walls. The leaching rates (LR) of treatments and the extractables remained low, between 0.05 and 2.4%. The equilibrium moisture content (EMC) decreased by 50% for the four treatments, compared to untreated beech wood.

In order to explore the extractives of conifers an effective and environmentally friendly method of extraction with aqueous-alkaline solution allowing to isolate up to 10.4% of extractive substances (ES) from pine wood greenery and up to 6.9% from larch wood greenery was investigated. The component fractional composition of aqueous-alkaline extracts was studied. The antioxidant fraction activity of neutral and acidic components isolated from the produced extracts was evaluated. It was found that these fractions have a high antioxidant activity, where the activity of larch extract components was higher than that of the respective components of pine extract. Due to their rich chemical composition and high biological activity, extracts of pine and larch wood greenery produced by aqueous-alkaline extraction have good application prospects as biologically active preparations.

Bark wastes today are viewed as a high-value resource for biorefinery due to their chemical richness and diversity. This work presents a comprehensive chemical characterization of the inner bark and the outer bark of Eucalyptus camaldulensis cultivated in Algeria. The extractives were first isolated with an Accelerated Solvent Extractor (ASE) and then analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The content of pre-extracted bark in cellulosic polysaccharide and free sugar monomers was determined by Gas Chromatography (GC). The hemicellulose composition and amount was determined after the acid methanolysis and GC. The amount of lignin was determined gravimetrically by the Klason lignin method and the acid soluble lignin was determined by the UV method. Formic and acetic acids in the bark were determined by HPLC after alkaline hydrolysis. It was found that the extractives content were similar in the outer bark (0.85%) and the inner bark (0.88%). The cellulose content was higher in the outer bark (33.4%) than in the inner bark (28.7%). Lignin and the total hemicellulose contents were more abundant in the outer bark (31.7, 26.2%) than in the inner bark (28.6, 19.3%) whereas, sugar monomers were more abundant in the inner bark (4.4%) than in the outer bark (3.8%). The variation in acetic and formic acids and ash contents between the outer bark (1.5, 0.006 and 2.5%) and the inner bark (1.3, 0.005 and 2.4%) was small. The obtained results showed that the bark can be considered a suitable feedstock for lignocellulosic biorefinery and also for the extraction of bioactive compounds that can be used in different sectors.

A small library of 6-substituted syringyl model compounds with aliphatic, carboxylic, phenylic, benzylic alcohols and brominated substituents were prepared. The influence of the substituents on the chemical shifts of the compounds was analyzed. All of model compounds showed a characteristic increase in the 13 C NMR chemical shift of the methoxy group vicinal to the substitution. This 13 C NMR peak and its corresponding correlation peak in HSQC could potentially be used to identify 6-condensation in syringylic lignin samples.

Lightweight materials with high electrical conductivity and hydrophobic mechanical properties are ideal materials for electromagnetic interference (EMI) shielding. Herein, the conductive composites with great EMI shielding effectiveness (SE) were successfully obtained by introducing multi-walled carbon nanotube (CNT) and polydimethylsiloxane (PDMS) based on the original structure of natural wood (NW). CNT@PDMS/NW composites were prepared via vacuum-pulse impregnation method and characterized by Fourier transform infrared (FTIR), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) patterns, hydrophobicity analysis, and EMI shielding performance. As demonstrated, CNT nanosheets were successfully inserted into wood matrices, and hydrogen bonding between CNT nanosheets and cellulose nanofibers induced the fabrication of CNT@PDMS/NW composites. CNT@PDMS/NW composites exhibited excellent EMI SE values of 25.2 dB at the X-band frequency.