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.

     

Microstructure,strength and structural integrity of heat-treated beech and spruce wood

Abstract

Heat treatment of wood is an effective method by which to improve the dimensional stability and biological durability, but the mechanical strength is decreased at the same time. Besides chemical modification of cell-wall constituents, physical weakening of the microstructure owing to heat-induced defects may also contribute to strength loss. Therefore, anatomical properties of heat-treated beech (Fagus sylvatica L.) and spruce (Picea abies Karst.), studied by light microscopic and scanning electron microscopic analysis, and their interrelation with strength properties and structural integrity were investigated. For determination of structural integrity, the high-energy–multiple-impact (HEMI) test was applied. Microscopic analyses showed frequent formation of radial cracks in heat-treated beech close to the rays as well as tangential cracks in the latewood of spruce. In addition, the modulus of rupture was more affected by the heat treatments than the resistance to impact milling (RIM) determined by the HEMI test, because RIM is based on multiple fractures on the microlevel that are not affected by the formation of intercellular cracks or other defects due to the heat treatment. It was concluded that heat-induced defects in the wood microstructure contribute to the substantial strength loss of thermally modified timber.     

Evaluation of thermally modified beech and spruce wood and their properties by FT-NIR spectroscopy

Quality assessment of thermally modified spruce (Picea abies (L.) Karst) and beech (Fagus sylvatica L.) wood and of the corresponding reference samples was carried out by means of non-destructive FT-NIR spectroscopic measurements and PLS regression. Oven-dry and basic density as well as MOE and MOR determined by 3-point bending tests were evaluated. The focus was put on specimens produced from material that had been thermally modified in an industrial scale kiln. Modelling results range from poor to very good. The results of the spectra taken from the spruce samples resulted in better prediction results than the spectra of the beech samples. This could be due to different proveniences or variation in the industrial modification process. The results indicate that FT-NIR surface measurements of sound thermally modified wood samples could be applied to evaluate several characteristics before and after the modification process. The method could be used for screening during pre-sorting of thermally modified wood.     

Alkaline degradation of wood: Effects on Young's modulus

Summary The influence of strong alkaline attack on the elastic modulus of beech wood was investigated from a physico-chemical point of view. It was shown that by treating rather large samples with 24% caustic potash solution, part of the hemicelluloses and lignin is removed; also wood shrinks more that three times as much as normally. This has no effect on the net cell wall elastic properties of the wood in spite of statements by other authors on milder treatment. It is supposed that such a treatment triggers a dissolution of the so-called sparingly-soluble hemicelluloses up to an extent by which wood is densified without loosing its structure. Further investigations will be carried out on the general properties of wood subjected to this kind of treatment.     

Influence of heat treatment on antioxidant properties and colour stability of beech and spruce wood and their extractives

Heat treatment of wood in absence of oxygen and under mild conditions allows for obtaining a material with many interesting properties, such as enhanced dimensional stability and increased biological durability. The aim of this work was to study the influence of a thermal treatment on the antioxidant activity of the extractives of two wood species – beech and spruce – by using the DPPH method and quantifying the formation of phenoxyl radicals using ESR as wood and extractives are exposed to light irradiation. The relationship between the kinetics of formation of free radicals in the extracts of heat-treated wood and the antioxidant properties is discussed. Links with colour modification are discussed.     

Silylation of solid beech wood

This report presents a new derivative from the chemical conversion of hardwood. Silylation of hardwood was successfully achieved using trimethylsilyl chloride with pyridine as base. The new wood compounds were analyzed by FTIR spectroscopy. The FTIR spectra of the silylated wood compounds show new absorption bands derived from trimethylsilyl ether groups. Furthermore, the products were investigated by means of EDX analysis. The presence of silicon confirmed the conversion of wood into the corresponding silyl ether derivative. Electron microscopy, i. e. SEM, shows that the location of the silicon was not restricted to the surface of the wood fibres. Penetration of the reactants into the wood body occurred, when a solid wood sample (beads) was used.     

Micromorphology of naturally degraded beech and spruce barks

The micromorphological changes occurring in the bark tissues of beech and spruce trees during natural degradation in the forest have been investigated and compared with those obtained previously using wood-decaying fungi. The relevance of the bark degradation process for the environment is also briefly discussed.     

Moisture-dependent orthotropic elasticity of beech wood

Elastic material properties are one of the most important material characteristics in mechanical modelling. Wood with distinctively different properties in the longitudinal, radial and tangential directions exhibits a strong moisture-dependent material characteristic in the elastic range. In order to characterise beech wood as an orthotropic material, all of the independent elastic properties were determined at different moisture conditions. These characteristic properties have never been determined before as a function of moisture content yet are vital to the field of wood modelling. All elastic parameters, except for some Poisson’s ratios, show a decrease in stiffness with increasing moisture content. In comparison to available literature references at a moisture content of ω?≈?12%, the identified values were of the same order of magnitude. The determined material properties can be used to investigate the mechanical behaviour of beech wood structures including different moisture conditions.     

Impact of water scarcity on spruce and beech forests

One of the greatest threats posed by ongoing climate change may be regarded the drought caused by changes in precipitation distribution. The aim of presented study was to characterize reactions to dry conditions and conditions without drought stress on gross primary production (GPP) and net ecosystem production (NEP) of spruce and beech forests, as these two species dominate within the European continent. Daily courses of GPP and NEP of these two species were evaluated in relation to an expected decrease in CO2 uptake during dry days. The occurrence of CO2 uptake hysteresis in daily production was also investigated. Our study was performed at Bily Kriz(spruce) and Stitna(beech) mountain forest sites during 2010–2012 period. We applied eddy covariance technique for the estimation of carbon fluxes, vapor pressure deficit and precipitation characteristics together with the SoilClim model for the determination of drought conditions, and the inverse of the Penman–Monteith equation to compute canopy conductance. Significant differences were found in response to reduced water supply for both species. Spruce reacts by closing its stomata before noon and maintaining a reduced photosynthetic activity for the rest of the day, while beech keeps its stomata open as long as possible and slightly reduces photosynthetic activity evenly throughout the entire day. In the spruce forest, we found substantial hysteresis in the light response curve of GPP. In the beech forest, the shape of this curve was different: evening values exceeded morning values.     

Aging law of spruce wood

Abstract

Accelerated aging of spruce wood samples have been carried out by thermo-hydro (TH) treatments. These treatments were applied to accelerate the chemical reactions that take place during the natural aging of wood. In order to avoid dissimilar chemical reactions between the TH treatments and the natural aging, mild temperatures (between 100 and 150°C) have been selected at low relative humidity (RH). The mechanical properties of non-aged, natural aged and accelerated aged spruce wood have been compared. It is apparent that longitudinal Young's modulus of accelerated aged wood increase slightly at the beginning of the treatment and is followed by a reduction. Along the radial direction, Young's modulus remains almost unchanged. On the other hand the radial strength is severely reduced. From these results, the relative radial strength has been fitted on the chemical kinetic law. The rate constant of this law has been calculated and the treatment temperature and wood moisture content have been integrated. Finally this law has been extrapolated to standard climatic conditions in order to predict the loss of strength of old wood by knowing its age and its mean climate history of temperature and RH (ambiance condition).     

Effect of heat treatment on extracellular enzymatic activities involved in beech wood degradation by Trametes versicolor

Effect of heat treatment on extracellular enzymes involved in wood degradation by Trametes versicolor was investigated. Heat-treated and untreated beech blocks were exposed to T. versicolor on malt-agar medium and extracellular enzymatic activities investigated. A strong ABTS oxidizing activity has been detected during the first stage of colonization in both cases, while cellulase activities are mainly detected in the case of untreated beech wood. Further investigations carried out on holocellulose, isolated using sodium chlorite delignification procedure and subjected to heat treatment or not, indicate that commercially available cellulases and xylanases are able to hydrolyse untreated holocellulose, while heat-treated holocellulose was not affected. All these data suggest that chemical modifications of wood components during heat treatment disturb enzymatic system involved in wood degradation.     

Tartaric acid catalyzed furfurylation of beech wood

European beech (Fagus sylvatica L.) is a major tree species of European forest which is underexploited because of its low dimensional stability and durability. Similarly to what has been developed with radiata pine, furfurylation might be the answer to optimize the utilization of local beech wood. Beech wood furfurylation process was studied using five different catalysts: maleic anhydride, maleic acid, citric acid, itaconic acid, and tartaric acid. Optimization of the furfurylation process was investigated for different catalyst and furfuryl alcohol (FA) contents, and different duration of polymerization. The following properties were studied: weight percent gain (WPG), leachability, anti-swelling efficiency (ASE), wettability, modulus of elasticity, modulus of rupture, Brinell hardness, and decay durability. Tartaric acid, never investigated up to now, was retained as catalyst to perform furfurylation due to its efficacy compared to other catalysts and its novelty. Wood modification with FA and tartaric acid as catalyst led to samples with high WPG even after leaching, improved ASE, and lower wettability with water. Increasing the polymerization duration increased the fixation of FA in treated wood. Most of all, treatment gave a significant improvement in mechanical properties and resistance to wood decaying fungi.     

Properties and set-recovery of surface densified Norway spruce and European beech

The chemistry and wetting behaviour of surface densified wood were investigated using FT-IR spectroscopy and contact angle analyses. Furthermore, set-recovery of the surface under conditions of fluctuating humidity was measured and quantitative microscopy analyses were undertaken. FT-IR indicated that no significant chemical changes took place during the densification process. However, the wettability of the densified surfaces was significantly lower than unmodified surfaces. Following several high humidity-oven dry cycles, it was found that this densification process was almost completely reversible, i.e., there was full set-recovery.     

Adhesive penetration in beech wood: experiments

A study with synchrotron radiation X-ray tomographic microscopy (SRXTM) of PUR, PVAc, and UF adhesive bond lines in beech wood, bonded under various growth ring angles, is presented. The bond line morphologies and the adhesive penetration into the wood structure were evaluated after determining the hardening characteristics of the adhesives. Distinct bond line imperfections were found for the different adhesive systems. To describe the adhesive distribution inside the bond line, the saturation of the pore space instead of the commonly used maximum penetration depth seems to be adequate.     

Liquefaction of beech wood in various supercritical alcohols

The liquefaction of Japanese beech (Fagus crenata Blume) was studied with various straight-chain alcohols in subcritical and supercritical states using a batch-type reaction vessel to obtain liquid fuel from lignocellulosics. Under the reaction condition of 270°C, beech wood was liquefied to some extent in all alcohols with about 50%–65% insoluble residue left after treatment for 30min. Under the condition of 350°C, however, more than 90% of wood was decomposed and liquefied in all alcohols. Alcohols with longer alkyl chains liquefied lignocellulosics in shorter reaction times. Because many kinds of alcohols, such as methanol and ethanol, can be produced from biomass, 100% biomass-based liquid fuel can be prepared by supercritical alcohol technology when using such bioalcohols. This study was presented in part at the 55th Annual Meeting of the Japan Wood Research Society, Kyoto, Japan, March 16–18, 2005     

Measuring compression wood severity in spruce

As the severity of compression wood influences the mechanical and chemical properties of wood it is desirable to be able to measure compression wood severity. However, so far no satisfactory method has been reported in the literature. Here we describe how scanning FTIR micro-spectroscopy can be employed to achieve CW severity measurements on increment cores of Norway spruce (Picea abies (L. Karst.) and Sitka spruce (Picea sitchensis (Bong.) Carrière). Radial wood strips were converted into sawdust by a process that maintained their spatial orientation. Samples prepared in this way were scanned with an FTIR-microscope in reflective mode and from the spectra obtained a CW-indicator was calculated representing aromatic and carboxyl signals. This FTIR CW-indicator correlated well with alternative CW identification techniques (namely microfibril angle, transmitted light and immunolabelling of beta 1–4 galactan), which have been used to validate the method. Repeatability of the measurements was good and no systematic difference between spruce species was found. The achievable resolution of the measurements was of sub-mm order. The CW indicator described offers the opportunity to correlate CW severity with mechanical wood properties in spruce.     

Thioacidolytic analysis of residual lignins isolated from the chemical pulps of spruce (Picea abies) and beech (Fagus sylvatica) wood

Eight different residual lignins isolated from unbleached chemical pulps [sulfite, kraft, alkaline sulfite-anthraquinone-methanol (ASAM), soda/AQ/MeOH] of spruce and beech were characterized using gel permeation chromatography (GPC), thioacidolysis, and desulfurization to determine average molecular weight, amounts of uncondensed β-O-4 linkages, and dimeric linkage patterns, respectively. The total amounts of G-CHSEt-CHSEt-CH₂SEt and S-CHSEt-CHSEt-CH₂SEt were markedly reduced in residual lignins to 40% to 80% of the values for the corresponding milled wood lignins (MWLs). The number of dimeric units determined by thioacidolysis and desulfurization of the residual lignins was decreased by onehalf to one-fifth compared to the MWLs. Among the diverse types of dimeric units, reduction of β-1 and β-5 units was significant in most of the residual lignins, with the exception of beech ASAM residual lignin. Compared to beech MWL, 40% more C6–C3 main monomers were detected, whereas the relative composition of the dimeric units in the beech residual lignin was very similar to that in the beech MWL. The average molecular weights of residual lignins were less than those of the MWLs. However, the average molecular weights of the spruce kraft and soda residual lignins were determined to be higher than those of the corresponding MWLs.     

Chemical changes during the production of thermo-treated beech wood

Thermal treatments of beech wood with different temperature loads on the wood cause characteristic changes in the chemical composition. The determination of specific changes was carried out by means of suitable methods, both wet chemical and instrumental analyses. It could be confirmed that in addition to the degradation of polyoses, lignin, known as the thermally most stable compound, shows significant thermal alterations too.     

Polyphenols in the woody roots of Norway spruce and European beech reduce TTC

A common method to determine the vitality of fine root tissue is the measurement of respiratory activity with triphenyltetrazolium chloride (TTC). The colorless TTC is reduced to the red-colored triphenyl formazan (TF) as a result of the dehydrogenase activity of the mitochondrial respiratory chain. However, measurements with woody fine roots of adult Norway spruce and European beech trees showed that dead control roots had a high potential to react with TTC. High reactivity was found in boiled fine roots and the bark of coarse roots, but not in the boiled wood of coarse roots. By sequential extraction of dried and ground adult Norway spruce fine roots, reactivity with TTC was reduced by about 75% (water extraction), 93% (water/methanol extraction) and 94% (water/acetone extraction). The water extract reacted with TTC in the same way as polyphenols such as lignin, catechin and epicatechin. Boiling did not affect the extent to which fine roots of adult trees reduced TTC, whereas it greatly reduced TTC reduction by seedling roots. Application of the TTC test to roots of spruce seedlings subjected to increasing drought showed a progressive decrease in TTC reduction. The decrease in TTC reduction was paralleled by a reduction in O(2) consumption, thus supporting the conclusion that for roots with a low polyphenol content the TTC test provides a valid assessment of tissue vitality. Our results suggest, however, that the TTC test should not be applied to the fine roots of adult trees because of their high content of polyphenolic compounds whose reaction with TTC masks changes in TTC reduction due to changes in the respiratory capacity of the tissue.     

A comparison of litterfall and element fluxes in even aged Norway spruce,sitka spruce and beech stands in Denmark

Litterfall was investigated in three even-aged Norway spruce (Picea abies), sitka spruce (Picea sitchensis) and beech (Fagus sylvatica) stands on a nutrient poor-soil in Southern Denmark. Dry weights and N, P, K, S, Mg, Ca, Na, Al, and Fe concentrations and fluxes were examined in litterfall fractions. Foliage litter amounted to 90% of total litterfall. The tree stands showed a similar mean annual litterfall. In the spruce stands, annual litterfall was correlated negatively with the current year increment and positively with the previous year increment. Annual litterfall in beech was constant during the 6 study years whereas Norway spruce and sitka spruce showed large fluctuations between years caused by drought, spruce aphid infestations and probably sea salt stress. Norway spruce responded with a long lasting elevated needle loss. Sitka spruce responded to infestations with premature needle loss during short periods. The presence of a large syrphid (Coccinellidae) population was important in regulating aphid (Elatobium abietinum) population density. The between-year variation in element concentrations of litterfall was small whereas variations during the year were large. Interspecific levels were recognized: Norway spruce>beech>sitka spruce. High concentrations in Norway spruce were ascribed to a combination of drought, sea salt stress and elevated transpiration. In sitka spruce, aphid infestations reduced the litterfall N content. Sitka spruce showed the smallest amount of base cation fluxes with litterfall. In contrast, spruce and beech exhibited even litterfall element fluxes. Litterfall studies revealed reduced vitality in the non-native spruce stands and underlined the perception of a healthy stand of native beech.