Changes of chemical properties and the water vapour sorption of <Emphasis Type="Italic">Eucalyptus pellita</Emphasis> wood thermally modified in vacuum

The aim of this study was to evaluate the chemical composition and the dynamic water vapour sorption properties of Eucalyptus pellita wood thermally modified in vacuum. For this purpose, wood samples were thermally modified in a vacuum oven at 160–240 °C for 4 h. Chemical composition were investigated by wet chemical analysis, elemental analysis, as well as Fourier transform infrared (FTIR) analysis, and dynamic water vapour sorption properties were evaluated by dynamic vapour sorption apparatus. The results showed that holocellulose and alpha-cellulose contents decreased and lignin and extractives contents relatively increased during the heat process. Elemental analysis showed a reduction in hydrogen content and an increase in carbon content. FTIR analysis indicated that the degradation of hemicellulose and condensation reactions of lignin occurred. In addition, the thermo-vacuum resulted in a reduction in the equilibrium moisture content of wood during the adsorption or desorption process. And the sorption hysteresis had a decreasing trend with increasing treatment temperature. The development of the hygroscopicity was related to the increase in the relative content of lignin, the degradation of the carbonyl groups in xylan and the loss of carbonyl group linked to the aromatic skeleton in lignin after heat treatment.     

Reactivity of lignin in supercritical methanol studied with various lignin model compounds

Behavior of lignin in supercritical methanol (250–270°C, 24–27 MPa) was studied by using lignin model compounds at the tin bath temperature of 270°C with a batch-type reaction vessel. Guaiacol and veratrole were selected as a guaiacyl type of aromatic ring in lignin, while 2,6-dimethoxyphenol and 1,2,3-trimethoxybenzene as a syringyl one. In addition, biphenyl and β-O-4 types of dimeric lignin model compounds were, respectively, studied as condensed and ether linkages between C₆-C₃ phenyl propane units. As a result, both guaiacyl and syringyl types of aromatic rings were very stable, and the biphenyl type was comparatively stable under supercritical conditions of methanol. However, β-ether linkage in the phenolic β-O-4 model compound was cleaved rapidly into guaiacol and coniferyl alcohol, which was further converted to its γ-methyl ether. Non-phenolic β-O-4 model compound was, on the other hand, converted initially into its α-methyl ether and degraded further to produce guaiacol. These lines of evidence imply that in lignin macromolecules, the new phenolic residues are continuously formed and depolymerized repeatedly in supercritical methanol into the lower molecular products, mainly by the cleavage of the dominant β-ether structure in lignin.     

Recycled ionic liquid 1-ethyl-3-methylimidazolium acetate pretreatment for enhancing enzymatic saccharification of softwood without cellulose regeneration

In this work, pretreatment of wood meals using a recycled ionic liquid (IL), 1-ethyl-3-methylimidazolium acetate ([Emim]Ac), enhanced glucose liberation by enzymatic saccharification, without dissolution of cellulose and lignin. In contrast, previous studies on IL pretreatment have mostly focused on lignocellulosic dissolution to regenerate cellulose and removing lignin. Softwood (Cryptomeria japonica) was pretreated with [Emim]Ac at 60–100 °C for 2–8 h without collecting regenerated cellulose. The pretreatment did not have a strong effect on wood component dissolution (weight of residues: 91.7–98.8%). The residues contained relatively high amounts of lignin (26.6–32.6%) with low adsorption of [Emim]Ac (0.9–2.7%). Meanwhile, the crystallinity index (C _r I) of cellulose in the wood was significantly reduced by pretreatment, from 50.9% to 28.4–37.1%. In spite of the high lignin contents in the residues, their glucose liberation values by enzymatic saccharification using a cellulase mixture were 3–16 times greater than that of untreated wood. A good correlation was found between the saccharification effectiveness of pretreated samples and the C _r I. Although lignin dissolved in [Emim]Ac continued to accumulate after repeated use of [Emim]Ac, the pretreatment was found to be effective for three consecutive cycles without the need to remove the dissolved materials.     

A literature-based study on the loss tangent of wood in connection with mechanical pulping

In mechanical pulping, wood is dynamically loaded, which causes large heat losses due to wood viscoelasticity. The heat losses depend on the loss tangent (tan δ) of wood. The loss tangent has a temperature-dependent behaviour, especially in the lignin glass transition region. The glass transition softens wood, and is therefore necessary for gentle mechanical pulping, but at the same time, the loss tangent shows a maximum called the α-peak. The transient peak depends on temperature, loading frequency and moisture content. The temperature where the peak is found can be lowered with chemical treatments, but they also increase the magnitude of the peak. Thermal treatment in the presence of water also increases the magnitude. The loss tangent of wood depends, amongst other things, on the chemical structure of lignin, width of cellulose crystals, microfibril angle, and extractives in the cell wall.     

Impact of thermal modification on color and chemical changes of spruce and oak wood

Thermal modification of wood is an environment-friendly alternative method for improving several properties of wood without the use of chemicals. This paper deals with the examination of color and chemical changes in spruce (Picea abies L.) and oak wood (Quercus robur F.) that occur due to thermal treatment. The thermal modification was performed at 160, 180, and 210 °C according to thermowood process. The color changes were measured by the spectrophotometer and described in the L*a*b* color system. Chemical changes were examined by wet chemistry methods, infrared spectroscopy and liquid chromatography. During the experiment, oak samples showed smaller color changes than spruce samples at all temperature values. During thermal modification, the content of cellulose, lignin, and extractives increases; however, the hemicellulose content drops by 58.85% (oak) and by 37.40% (spruce). In addition to deacetylation, new carbonyl and carboxyl groups are formed as a result of oxidation. Bonds in lignin (mainly β-O-4) and methoxyl groups are cleaved, and lignin is condensed at higher temperatures.     

Bromination of different morphological parts of spruce wood (Picea abies)

Summary It has been found that the lignin in a middle lamella fraction isolated by a sieving technique has the same reactivity to bromine as the whole wood lignin. A plataue value of 1 mole bromine/mole C₉-unit was obtained for both samples. The lignin in compression wood had a considerably lower reactivity to bromine than the normal wood lignin. A plataue value of 0.68 mole bromine/mol C₉-unit was obtained with such lignin. The discrepancy between this and earlier results from the bromination of middle lamella and the implication of the results for lignin determination by the SEM- and TEM-EDXA technique are discussed.     

Kinetic analysis of color changes in keyaki (Zelkova serrata) and sugi (Cryptomeria japonica) wood during heat treatment

The kinetics of color changes in keyaki (Zelkova serrata Makino) and sugi (Cryptomeria japonica D. Don) wood during heat treatment were examined. The color of wood specimens treated at 90, 120, 150, and 180 °C was measured by an imaging spectrophotometer and expressed using CIELAB color parameters. At any treatment temperature, values for L* and $ \Updelta E_{ab}^{*} $ decreased and increased in both wood species, respectively, with increased treatment time. Changes in a* and b* varied depending on wood species and treatment temperature. The color changes were successfully analyzed using the kinetic approach applying time–temperature superposition method. This approach elucidated and accurately predicted color changes during heat treatment.     

Effect of severe thermal treatment on spruce and beech wood lignins

? The structure, proportion and mode of assembly of lignin, celluloses and hemicelluloses have marked effects on the reaction mechanisms during thermal treatment and therefore have a strong influence on the quality of the final product. The effect of treatment conditions, including severe conditions (up to 553 K) and treatment duration (up to 8 h) on the structure of native spruce and beech lignins was studied.

? Lignin content was determined by the Klason method and lignin structure was evaluated by thioacidolysis.

? The results highlighted the strong reactivity of the native spruce and beech lignins towards severe heat treatments. The distinct susceptibility of syringyl (S) and guaiacyl (G) units towards thermal treatment is confirmed by comparing the data for beech and spruce samples. The most severe treatment of spruce wood (280 °C) induced a dramatic enrichment in lignin content together with the almost complete disappearance of G lignin units, whereas a more moderate treatment substantially changed lignin structure by degradation reactions that affect the p-hydroxyphenyl (H) and G lignin units similarly.

? Thioacidolysis revealed that the thermal treatment induces the appearance of vinyl ether structures in spruce lignins. The decreased yield of the G and S thioacidolysis monomers reflects the progressive disappearance of G and S lignin units only involved in β-O-4 bonds and the formation of condensed linkages in proportions related to treatment severity. In severe conditions, β-O-4 linked S units are more degraded than their G homologues.

     

Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC1₃. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC1₃. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin.     

Elastic modulus of lignin as related to moisture content

The Young's and shear moduli of two lignins have been measured at several moisture contents. Cylindrical test specimens moulded from periodate and Klason lignin powders were conditioned to the required moisture contents and tested in tension and torsion. The Young's modulus of periodate lignin increased linearly from 3.1x10⁹ to 6.7x10⁹ Pa, and the shear modulus from 1.2x10⁹ to 2.1x10⁹ Pa as the moisture content of the lignin decreased from 12 to 3.6%. Klason lignin showed similar behaviour but its moduli were always much lower. This was probably a consequence of the more drastic alteration undergone by the Klason lignin during its isolation from the wood cell wall.I am indebted to Messrs M. B. Forsyth and L. P. Lowe for assistance with the design and construction of the testing equipment used in this work.     

Element content and pH value in American black cherry (<Emphasis Type="Italic">Prunus serotina</Emphasis>) with regard to colour changes during heartwood formation and hot water treatment

Element content and pH value in wood tissues of veneer grade logs of P. serotina Ehrh. were investigated with regard to wood colour variations, measured in the CIEL*a*b* system. The average pH value of heartwood tissue was about pH 4.0 and medium colour parameters of veneer sheets were determined at L* = 73, a* = 9.8, and b* = 23.5. Optical emission spectroscopy (ICP-OES) analyses showed differences in the element contents between two regional forest sites coming from Pennsylvania and West Virginia, USA, respectively. The latter is mainly characterised by higher variations of micro-element content in the transition zone (influencing heartwood formation) and also pH value of wood tissue, which contributes to higher variations in colour response of industrially produced veneer sheets. Investigations under industrial conditions underline the correlation between length and intensity of heat treatment in veneer production and colour development: with increasing duration and temperature of hot water treatment, veneer surfaces become darker and wood colour is intensified (ΔL = 3.6, Δa = 2.1, comparing 12 and 72 h of hot water treatment at 60°C). However, no equalisation of wood colour was achieved by modifying the treatment conditions. Artificial radiation by UV–visible light, quickly and extensively darkens and intensifies wood colour (ΔL = 16, Δa = 3.5, and Δb = 4.0 after 15 h of artificial radiation), but variations in wood colour deriving from different treatment conditions during veneer production, were not reduced.     

Characterization of lignin-derived products from Japanese beech wood as treated by two-step semi-flow hot-compressed water

Japanese beech (Fagus crenata) wood was treated by two-step semi-flow hot-compressed water (the first stage: 230 °C/10 MPa/15 min, the second stage: 270 °C/10 MPa/15 min), and produced lignin-derived products in the hot-compressed water-soluble portions at the first and second stages, and the final residue of the second stage was characterized with alkaline nitrobenzene oxidation method and gel permeation chromatographic analysis. As a result, the lignin-derived products at the first stage, where hemicellulose was also decomposed, consisted of lignin-based monomers and dimers and oligomers/polymers in the water-soluble portion. A large part of the oligomers/polymers was, however, recovered as the precipitate during 12 h setting after hot-compressed water treatment. By the analysis of nitrobenzene oxidation products, there were relatively higher contents of ether-type lignin in the precipitate at the first stage than in original beech wood. Since the ether linkages of lignin are more preferentially cleaved by this hot-compressed water, lignin-based polymeric fractions were flowed out from the porous cell walls from which hemicellulose was removed. On the other hand, at the second stage condensed-type lignin remained in the precipitate and residue. Based on these results, decomposition behavior of lignin in Japanese beech wood as treated by the two-step semi-flow hot-compressed water was discussed regarding the topochemistry of lignin structure.     

Response of colour and hygroscopic properties of Scots pine wood to thermal treatment

The effect of heat treatment on the surface colour and hygroscopic properties of pine wood were investigated in this study. Boards of Scots pine wood (Pinus sylvestris L.) were subjected to thermal treatment at 200°C, for 4, 6, and 8 h. The change of equilibrium moisture content and density values of the specimens in order to facilitate the understanding of the treated material behavior. The colour parameters L*, a* and b*, used to depict the total colour change (Δ E) of wood surface, were shown to change proportionally to the treatment intensity. Moreover, swelling in the tangential and radial directions and absorption of the specimens appeared to be enhanced in great extent by the thermal treatment process. The mean value of swelling percentage in the tangential direction decreased 10.26%, 17.22%, and 19.60% for specimens treated for 4, 6, and 8 h, respectively, referring to the final measurement after 72 h of immersion. In radial direction, mean value of swelling percentage decreased 19.56%, 32.75%, and 34.65% for treated for 4, 6 and 8 h, respectively, after 72 h immersion, which attests the decrease in swelling and improvement in the hygroscopic behavior of Scots pine wood.     

An irreversible thermodynamics model for unsteady-state nonisothermal moisture diffusion in wood

Summary A model that predicts heat and moisture transfer through wood in the hygroscopic range and which is based on the principles of irreversible thermodynamics, was evaluated with unsteady-state nonisothermal moisture desorption experimental data. The model predicted the phenomenon of thermal diffusion during the initial stages of desorption and results in a very good simulation of the desorption curve and the center's temperature change with time.Symbols C_p specific heat of air (= 0.24 cal/g K @ 70 °C) - C_T specific heat of wood, cal/g K - D transverse diffusion coefficient, cm²/s - E_b activation energy, cal/mol - E_o heat of vaporization, cal/mol - E_L differential heat of sorption, cal/mol - G specific gravity of wood - H relative humidity, % - h_T convective heat transfer coefficient, cal/cm² s K - h_c convective mass transfer coefficient based on the concentration of moisture in wood, cm/s - h_v convective mass transfer coefficient based on the concentration of moisture in the air in equilibrium with the wood surface, cm/s - K_M coefficient for diffusion due to moisture gradient, g/cm s % - K_T transverse thermal conductivity coefficient, cal/cm K s - M moisture content, % - P_o saturated vapor pressure, atm - R universal gas constant, cal/mol K (= 82.056 cm³ atm/mol K) - t time, s - T temperature, K - x distance, cm Greek Letters evaporation or condensation criterion - wood density, g/cm³ - _W water density (=1), g/cm³ - _a air density, g/cm³ Department of Wood Science and Forest Products Virginia Polytechnic Institute and State University Blackburg, Virginia 24061-0503     

Spectroscopic analysis of the role of extractives on heat-induced discoloration of black locust (Robinia pseudoacacia)

Abstract

To investigate the role of extractives on heat-induced discoloration of wood, samples of black locust (Robinia pseudoacacia) wood flour were extracted with various solvents prior to heat-treatment. Analysis of their color parameters and chromophoric structures showed that the chroma value of the unextracted sample decreased while that of the extracted sample increased after heat-treatment. Both samples showed broad diffuse reflectance UV-Vis (DRUV) absorption bands with maxima around 360–380 nm after heat-treatment due to the formation of conjugated double bonds, carbonyl functionalities, and quinoid structures. Compared with the unextracted sample, the dominant chromaticity of the extracted samples hypochromatically shifted and the peak became narrower. This result showed that extractives contribute mostly to the reduction in the light reflection on heat-treated wood. In addition to extractives, lignin and hemicellulose also contributed to the formation of color substances upon heat-treatment. The increase in C₃/C₂ ratio in X-ray photoelectron spectroscopy (XPS) spectra signified the oxidation reactions in the heating process. The increase in O₁/O₂ for extracted sample after heat-treatment and changes in DRUV and Fourier transform infrared spectroscopy (FTIR) spectra support the hypothesis that discoloration can also arise from the degradation of hemicellulose and the condensation reactions of lignin.     

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.Part of this report was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003     

Effect of extractives on conferred and natural durability of Cupressus lusitanica heartwood

? Identification of extractives present in Cupressus lusitanica heartwood has been conducted using GC-MS analyses. The chromatogram of toluene/ethanol extracts indicated the presence of large amounts of benzaldehyde and numerous terpenic compounds such as cedrol, agathadiol, epimanool, bornyl acetate, α-cedrene and β-cedrene.

? The effect of these extractives on the natural durability of cypress wood was investigated on heart wood blocks exposed to pure culture of Poria placenta before or after solvent extraction. Weight losses revealed severe fungal degradations on the extracted blocks compared to unextracted ones.

? Efficiency of heartwood extractives as inhibitors of the growth of Poria placenta on malt/agar test confirms their contribution to cypress natural durability.

? Cypress blocks were treated at 240 °C for different times to reach different levels of thermodegradation to evaluate effect of heat treatment on fungal durability. Results indicate that evaporation of volatile extractives during the first few minutes of heat treatment contribute to decreased wood durability, while longer treatment times lead to the expected improvement of durability.

? This study suggests that the content of extractives, which may be modified during wood drying or weathering processes, could be the origin of the conflicting data described in the literature concerning cypress natural durability.

     

Consumption of O<Subscript>2</Subscript>, evolution of CO<Subscript>2</Subscript> and reduction of Cr(VI) during fixation of chromium based wood preservatives in wood

Norway spruce dust was impregnated with aqueous solutions of chromated copper wood preservatives. Immediately after treatment, observation of CO₂ evolution and O₂ consumption were performed. Significant quantities of CO₂ were released during reaction of chromium (K₂Cr₂O₇) containing solutions with wood or brown rotted wood. Nevertheless, during reaction of cellulose with these preservatives we did not observe evolution of CO₂. The presence of copper did not influence on concentration of CO₂. Opposite to CO₂ evolution, treatment of wood and brown rotted wood resulted in O₂ consumption. The oxygen concentration decrease in the measuring chamber was approximately 5 times greater than increase of concentration of carbon dioxide. Electron paramagnetic resonance (EPR) observations of chromium fixation showed that chromium is reduced from Cr(VI) to Cr(III) with Cr(V) as an intermediate on wood, brown rotted wood and cellulose. However, the reduction on wood and brown rotted wood was faster than the reduction on cellulose, as determined from changes of Cr signals in EPR spectra. So, evolution of CO₂ and consumption of O₂ as well as EPR signals of Cr species thus indicate that brown rotted wood, consisting of lignin and hemicelluloses in contact with Cr(VI) reacts more intensively than cellulose, and possibly, oxidation mechanisms of lignin and cellulose with Cr(VI) are different. Received: 20 July 2000     

高温热处理对桃花心木化学性质的影响

热处理是木材加工行业中常用的处理手段之一,可有效提升木材尺寸稳定性及具有防生物侵蚀能力,但在一定程度上也会降低木材的力学性能.热处理导致木材材性变化的根本原因是木材组分含量及其分子结构在热量作用下发生了变化.笔者探索了不同热处理温度下(150,165,180,195和210℃)桃花心木材的化学组分变化.结果表明:经热处...     

Interaction of lignin and polysaccharides in beech wood (Fagus sylvatica) during drying processes

Summary ¹³C CP MAS NMR spectroscopy was used to characterize the structural changes of cell wall polymers in beech wood Fagus sylvatica during drying processes. The analysis of five wood samples, namely, untreated, untreated dried, pre-treated by steam and/or NaOH subjected to drying showed partial depolymerization of lignin component as well as the change of the ratio of the crystalline and of the amorphous parts of cellulose as the consequence of wood pre-treatment. In addition, T_1ρ(¹H) relaxation times were determined in beech wood sample pre-treated with steam at 135 °C and the lignin isolated from this sample. The magnitudes of the relaxation times were found comparable in both samples as well as in the lignin-cellulose model compound. These unique T_1ρ (¹H) values indicate that spin diffusion is complete and homogeneous due to spatial proximity of spins and confirmed the formation of lignin-cellulose complex during thermal treatment of wood. Received 30 June 1997