Effect of heat treatment intensity on some conferred properties of different European softwood and hardwood species

Effect of heat treatment intensity on some conferred properties like elemental composition, durability, anti-swelling efficiency (ASE) and equilibrium moisture content (EMC) of different European softwood and hardwood species subjected to mild pyrolysis at 230 °C under nitrogen for different durations has been investigated. Independently of the wood species studied, elemental composition is strongly correlated with the mass losses due to thermal degradations which are directly connected to treatment intensity (duration). In all cases, an important increase in the carbon content associated with a decrease in the oxygen content was observed. Heat-treated specimens were exposed to several brown rot fungi, and the weight losses due to fungal degradation were determined after 16 weeks, while effect of wood extractives before and after thermal treatment was investigated on mycelium growth. ASE and EMC were also evaluated. Results indicated important correlations between treatment intensity and all of the wood conferred properties like its elemental composition, durability, ASE or EMC. These results clearly indicated that chemical modifications of wood cell wall polymers are directly responsible for wood decay durability improvement, but also for its improved dimensional stability as well as its reduced capability for water adsorption. All these modifications of wood properties appeared simultaneously and progressively with the increase in treatment intensity depending on treatment duration. At the same time, effect of extractives generated during thermal treatment on Poria placenta growth indicated that these latter ones have no beneficial effect on wood durability.     

Treatment of timber with water soluble dimethylol resins to improve their dimensional stability and durability

Summary European Beech (Fagus silvatica L.) was impregnated with a dimethylol resin to improve its dimensional stability and durability. Different catalysts were evaluated in combination with the resin. Depending on the range of relative humidity, the resin improved the shrinkage and swelling by approximately 50%. The use of an acid (citric or tartaric) catalyst lead to improved resin curing. A curing temperature of 100 °C is necessary.The reported work has been part of an EEC Research Program (DGXII) and had been carried out by the author at TNO Timber Research Institute     

Acetylation of wood in combination with polysiloxanes to improve water-related and mechanical properties of wood

Scots pine sapwood was acetylated with ethyltriacetoxysilane using acetic acid as a solvent and sulfuric acid as a catalyst. A weight percent gain (WPG) of 14 % and cell wall bulking of 7 % were obtained after 5 h of reaction time. Pine specimens were acetylated with acetic anhydride in the presence of 1 % ethyltriacetoxysilane, dihydroxy-functional siloxane, acetoxy-functional siloxane, amino-functional siloxane and non-functional siloxane, respectively. Acetoxy-functional siloxane induced the greatest reduction in water uptake with a water repellent effectiveness after 24 h of up to 62 % as compared to acetylated wood. WPG and cell wall bulking increased compared to solely acetylated wood with increasing concentrations of acetoxy-functional siloxane in acetic anhydride; anti-shrink efficiency, however, did not increase. Fungal resistance of pine sapwood and beech as well as mechanical strength properties did not change when 20 % acetoxy-functional siloxane was added to acetic anhydride compared to solely acetylated specimens.     

Preparation of acetylated wood meal and polypropylene composites I: acetylation of wood meal by mechanochemical processing and its characteristics

Wood meals of Sugi (Cryptomeria japonica D.Don) passing 2.0 mm and retained on 1.0 mm mesh screens were milled along with acetic anhydride (AA) and pyridine as a catalyst in a high-speed vibration rod mill at ambient temperature. The weight percent gain (WPG) of the chemically modified wood was calculated based on the yield after washing with deionized water. The effects of amounts of AA and catalyst added, pulverization time, and saponification of the acetylated wood on WPG were examined. In addition, FT-IR analysis, and water vapor adsorption and desorption tests were performed as functions of the WPG. Increases in WPG, the acetyl contents of the acetylated wood after saponification, changes in the FT-IR spectra after pulverization, and the water vapor sorption isotherms showed that the one-step acetylation systematically modified the hydroxyl groups of the wood into acetyl groups. Up to 38 % WPG was obtained at 100 phr AA and 15 phr catalyst, and 120 min pulverization. Pulverization time and the amounts of AA and catalyst added to the wood meals could be adjusted to obtain acetylated wood meal with the desired WPG. These demonstrated that the mechanochemical acetylation is a method to prepare acetylated wood meals with high WPG at less reaction time and required AA addition.     

Wood modification with alkoxysilanes

Wood was treated with three different alkoxysilanes which are able to undergo a sol–gel process: tetraethoxysilane (TEOS), methyl triethoxysilane (MTES) and propyl triethoxysilane (PTEO). Two types of treatments were compared: impregnation of fibre saturated wood with monomeric silane solutions, and impregnation with pre-hydrolysed partly oligomeric silanes. Wood properties such as cell wall bulking, anti-swelling efficiency (ASE), moisture uptake and durability were more significantly improved in samples treated with monomeric silanes than in samples treated with oligomeric silanes. SEM-EDX mapping showed that this treatment resulted in a higher degree of silicon incorporation into the cell wall, although the weight percent gain (WPG) was lower compared to the treatment with pre-hydrolysed partly oligomeric silanes. The resistance against soil micro-organisms was enhanced in the initial phase of incubation especially in those samples treated with organo-functional-alkoxysilanes. In miniaturised block tests with the white-rot basidiomycete Trametes versicolor, an improved durability was observed within the test period. During an air conditioning step, a weight loss of the treated samples occurred which was accompanied by a reduction in bulking and ASE. The initial reduction of moisture uptake observed after treatment diminished almost completely. This effect was explained by an ageing of the gels in the wood cell wall which is a consequence of uncompleted hydrolysis and condensation of the silanes during the treatment.     

Chemical modification of wood by anhydrides without solvents or catalysts

Acetylated, propionylated, butyrylated, isobutyrylated, and hexanoylated woods were prepared at several temperatures. The reaction rate, dimensional stability, and changes in the ratios of specific gravity and dimensions in the tangential and radial directions were estimated. The reaction rate of propionylation was slow at temperatures under 90°C but increased with the temperature. The butyrylated, isobutyrylated, and hexanoylated woods showed little or no weight percent gain (WPG) and little or no antiswelling efficiency (ASE) below 110°C even for 24h, but they achieved significant WPG and ASE values at 140°C with a longer reaction time. The acetylated, propionylated, and butyrylated woods showed almost the same values for dimensional stabilization efficiency based on WPG (DSE). The specific gravity and dimensions ratios for acetylated, propionylated, and butyrylated woods compared to those of untreated wood increased with an increase in WPG.     

Modification of wood with silicon compounds. inorganic silicon compounds and sol-gel systems: a review

This review describes the treatment of wood with various inorganic silicon compounds. Among these compounds silicofluorides represent one of the long-known classes of wood preservatives based on silicon. Data on an organic fluorosilicon compound (silafluofen) are additionally presented. The mode of action of these fluorides is based on their biocidal action. Water glass, an alkali silicate, was able to enhance the durability of wood but showed some important drawbacks. Because of its high hygroscopicity and its high pH values, increased moisture absorption and strength loss of wood was frequently observed. Wood treated with tetraalkoxysilanes showed an enhanced dimensional stability, especially when the hydrolysis and the condensation of the silanes was controlled to react within the cell wall. Durability and fire resistance were improved to a certain degree and could be significantly enhanced by addition of boron compounds.Abbreviations ASE antishrink efficiency - CCA (preservatives based on) copper, chromium, arsenic - CSAS colloidal silicic acid solution - EDX energy dispersive X-ray analysis - EPMA electron probe X-ray microanalysis - HFOETMOS 2-heptadecafluorooctylethyltrimethoxysilane - MEE moisture-excluding efficiency - MoE modulus of elasticity - r.h. relative humidity - SAMS silicic acid monomer solution - SEM scanning electron microscopy - TEOS tetraethoxysilane/triethyl orthosilicate - TEP triethylphosphite - TGA thermogravimetric analysis - TMB trimethylborate - TMOS tetramethoxysilane - TMP trimethylphosphite - TPOS tetrapropoxysilane - WPG weight percent gain     

Potassium acetate-catalyzed acetylation of wood at low temperatures II: vapor phase acetylation at room temperature

Ezomatsu wood blocks were impregnated with potassium acetate (KAc) and then exposed to acetic anhydride vapor at 25°C and 120°C. The KAc-impregnated wood was rapidly acetylated at 120°C, and only 6 min was needed to achieve 20% weight percent gain (WPG). The WPG increased with increasing catalyst loading (CL), but it turned to decrease above 20% CL probably because the diffusion of acetic anhydride vapor was hindered by excess KAc depositing in the cell lumina. Thus, careful control of CL is necessary in the vapor-phase acetylation. KAc was also effective in catalyzing the vapor-phase acetylation at 25°C: the KAc-impregnated wood attained 20% WPG within 7 days, whereas the WPG did not exceed 10% even after 1 month in the uncatalyzed system. Irrespective of treatment methods, the hygroscopicity of wood was reduced and its dimensional stability was improved with an increase of WPG. These results confirm that the use of KAc simplifies the acetylation process at room temperature with minimal loss of acetic anhydride.     

Effect of wood species,digester conditions,and defibrator disc distance on wettability of fiberboard

Wettability of medium density fiberboard (MDF) surface affects paint or adhesive application and is, thus, of importance in the course of furniture manufacturing. This study investigated the effects of wood species, digester conditions and defibrator disc distance on the wettability properties. It was found that the wettability of the MDF significantly decreased with increasing the defibrator disc distance and increased with the increment in the severity of the digestion conditions. The highest wettability was found for samples made of beech wood having an average contact angle value of 74.5°, followed by poplar wood (76.5°), birch wood (79.7°), the mixture (1:1) of scots pine and beech wood (82.9°), and scots pine wood (86.4°), respectively.     

Development of chemometric models based on near infrared spectroscopy and thermogravimetric analysis for predicting the treatment level of furfurylated Scots pine

The use of furfuryl alcohol (FA) as a wood modification agent has been known for decades. An independent and reliable analytical method to determine the level of furfurylation is not available. This article reports the use of near infrared spectroscopy (NIR) and thermogravimetric analysis (TGA) to make partial least square prediction models for determining the furfurylation level (the percentage of FA polymer formed within the wood structure). A total of 115 individual samples of furfurylated Scots pine (Pinus sylvestris) originating from 115 production batches were used for modelling. As much as 81 samples were randomly selected for the calibration set and 34 samples for the validation set. Both NIR and TGA gave good predictions when validated by a separate test set. The r ² for NIR and TGA are 0.93 and 0.94, respectively, and the root mean square errors of predictions are 1.025 and 0.958, respectively. However, the number of principal components for the NIR and TGA models is two and six, respectively. The NIR method is preferred because only two principal components are used and sampling is fast.     

Technological properties of glulam beams made from hydrothermally treated poplar wood

In this research, technological properties of glulam beams made from hydrothermally treated poplar (Populus deltoides) wood were investigated. Poplar wood blocks with dimensions of 6 (r)?×?10 (t)?×?73 (l)?cm³ were cut and hydrothermally treated in a stainless steel reactor at temperatures of 140 and 160°C for a holding time of 30?min. The treated wood blocks were initially air seasoned and then they were dried in a semi-pilot scale vacuum dryer to achieve moisture content (MC) of 12%. Conditioning of the treated and the untreated wood blocks was done prior to adhesive bonding. Afterwards the glulam beams (4 ply) were manufactured using polyurethane. In order to evaluate the physico-mechanical properties of the beams, density, equilibrium moisture content, water repellent effect (WRE), anti-swelling effect (ASE), mass loss (ML), wettability as well as surface roughness due to the hydrothermal treatment were determined in the treated wood and delamination, bond shear strength, tensile strength, MC and moisture-induced stresses as well as strains in cross-section of the beams were determined in the glulam beams. The results revealed that density, ML, ASE, WRE, modulus of elasticity, modulus of rupture and delamination were increasing and the others were decreased due to the hydrothermal treatment.     

Potassium acetate-catalyzed acetylation of wood: extraordinarily rapid acetylation at 120°C

The catalytic effect of potassium acetate (KAc) on wood acetylation was investigated. Spruce wood specimens were impregnated with KAc and then heated in acetic anhydride at 120°C. The degree of acetylation was evaluated by the weight percent gain (WPG). In the presence of KAc, the reaction time to achieve a 20% WPG decreased by a factor of 200: 2 min was required in the KAc-catalyzed acetylation, while the uncatalyzed acetylation required at least 5 h. The hygroscopicity and dimensional stability of acetylated wood depended on the WPG irrespective of the treatment methods. This fact proved that KAc had no adverse influence on the dimensional stability of acetylated wood. As KAc is a cheap, water-soluble and non-toxic salt it can be a useful catalyst for the extraordinarily rapid acetylation of wood.     

PF树脂浸渍速生杉木的性能研究

速生杉木通过浸渍PF树脂并压缩改性后,力学性能得到大幅度提高,且随着树脂浓度和压缩率的增加而提高。增重率与真空度、浸渍压力、时间有关,并随着其增加而增大;抗胀(缩)率和阻湿率与树脂的浓度有关,当树脂浓度从0上升到10%时,ASE和MEE的值变化较大,当树脂浓度超过10%后趋于平缓;在树脂浓度相同的情况下,较大压缩的恢复率也相应较大,当树脂浓度低于10%时,随着浓度增加,恢复率急剧下降,浓度达到15%以上时,恢复率几乎没有变化。     

Physical properties and termite durability of maritime pine Pinus pinaster Ait., heat-treated under vacuum pressure

An original heat treatment performed under vacuum pressure was investigated. Maritime pine samples were treated at six different temperatures: 140, 160, 180, 200, 230 and 260°C. The physical and mechanical consequences, i.e. bending strength (MOR), modulus of elasticity (MOE), hygroscopic behaviour, equilibrium moisture contents and anti-swelling efficiency (ASE) were studied. A no-choice feeding test according to the NF EN 117 standard was achieved. Temperatures up to 200°C had no significant effect on wood properties. However, at 230 and 260°C, the decrease in MOR was severe, reaching 42.5 and 62.5%, respectively. Whatever the treatment conditions, wood samples were still highly degraded by termites, revealing no increase in their durability.     

苯甲基化木材溶液制备聚氨酯树脂工艺条件的研究

用苯甲基化木材溶液与甲苯二异氰酸酯(TDI)反应制备聚氨酯树脂。通过考察TDI的加入量、增塑剂种类、催化剂用量和木粉增重率等因素对制得的聚氨酯涂膜性能的影响，得出了用苯甲基化木材制备聚氨酯树脂的最佳工艺条件：增重率为63％～80％的改性木粉8g、TDI 14～16mL、二月桂酸二丁基锡0．4％、分子质量为400的增塑剂。在此条件下，涂膜的干燥时间、铅笔硬度、附着力等参数基本可以满足聚氨酯涂料国家标准(GB 1986)的要求。     

Preparation of acetylated wood meal and polypropylene composites II: mechanical properties and dimensional stability of the composites

Acetylated wood meals of Sugi (Cryptomeria japonica D.Don) wood were prepared by mechanochemical processing using a high-speed vibration rod mill. Weight percent gain (WPG) of the acetylated wood meals ranged from 7.0 to 35.5 %. Wood–plastic composites (WPCs) containing 50 % acetylated woods were produced by an injection molding technique. The polymer matrix used was polypropylene homopolymer. Maleic anhydride-grafted polypropylene (MAPP) was also used as a compatibilizing agent. The mechanical properties of WPCs in bending and tensile tests were independent of WPG of acetylated wood meals, and the test values for WPCs containing acetylated wood meals were lower than that of unmodified wood meal. The use of MAPP increased bending and tensile strength, but no effect on bending modulus was found. An increase in WPG significantly decreased water absorbability and thickness swelling of WPCs as measured by dimensional stability tests. These results demonstrated that mechanochemical processing is a promising technique for preparing WPC material with improved dimensional stability. The future challenge is to inhibit the decreases in mechanical properties of WPCs containing acetylated wood meals.     

Modelling the economically viable wood in the crown of European beech trees

Long-term forest development programs in Germany aim on an increase of close-to-nature broadleaf forest stands. This means that the economic importance of European beech is expected to increase. The economic potential of a tree basically consists of the stem as well as the economically viable wood volume in the crown. Due to the high morphological variability of European beech crowns, taper models are often not satisfactory for predicting the economically viable wood volume arising from crowns. Prediction models with a higher precision are recently still lacking. Aim of this study is thus the development of prediction model for the economically viable crown wood volume of European beech trees.We determined the distribution of the wood volume in the crown over the branch diameters using the multistage ‘randomized branch sampling’ method (RBS). The tree-specific wood volume distribution on the branch diameters were used to cluster all sampled trees into 3 groups. Additionally, we developed a method able to distinguish between economically viable and unviable crown branches. Basing on the RBS measurements as well as revenues and processing costs, we modeled the economically viable wood volume from the crown for each tree. To calculate the wood volume under bark, we parameterized a bark thickness function from disk samples of the trees.We showed that the European beech crowns could be clustered into 3 groups differing in their wood volume distribution. The economically viable wood volume in the crown significantly depended on this grouping parameter as well as diameter at breast height (DBH). By contrast, the total amount of wood in the crown only depended on DBH. The differing viable wood volumes in the crowns were thus explained by different wood distributions and not by differing total crown wood volume. To make the results applicable in practice forestry, the modelling results were used to develop a regression formula able to predict the economically viable wood volume in the crown depending on the DBH and the crown type. As the crown type can also be predicted via measurable tree covariates, the regression model of the viable wood volume in the crown can be used as a support tool for the management of European beech stands. Sensitivity analysis quantifies how harvest revenues and costs translate into different viable tree volume.     

酚醛树脂处理杨木、杉木尺寸稳定性分析

采用酚醛树脂浸渍处理人工林杨木、杉木,然后通过热压定型工艺制得表面密实化木材。对其尺寸稳定性的分析结果表明:处理试材的增重率、抗胀率和阻湿率随树脂浓度的增加而成比例增大,弦向和径向干缩率明显降低,在树脂浓度较低时变化较大,当达到一定量时变化趋于稳定。就压缩变形恢复率而言,当树脂浓度超过10%,压缩变形恢复率很小,说明表面密实化木材的压缩变形几乎被固定。     

人工林软质木材表面密实化新技术

采用一种新型木材改性处理剂，分别以改性异氰酸酯浓度5％、10％、15％、20％，对美国人工林火炬松（Pinus taeda）进行表面密实化处理。结果表明，随着树脂浓度的增加，无论是冷水浸泡还是煮沸，木材的吸水厚度膨胀率和压缩变形恢复率明显降低。表面密实化后，火炬松处理材的MOR和MOE值分别比素材提高43．9％和30．1％；水浸24h和煮沸2h后的湿状抗弯性能比素材略低，干状抗弯性能明显比素材高，MOR分别高28．0％和25．76％；MOE分别高22．55％和27．79％。改性异氰酸酯浸渍处理后的表面密实化木材，具有一定的阻燃效果；表面耐磨耗性能和表面硬度亦明显改善。     

Properties of Esterified Wood Prepared with Maleic Anhydride ／ Tetrabr Omophthalic Anhydride ／ Glycerol Mixture

For overcoming disadvantages of wood, an esterification process was employed and tetrabromophthalic anhydride (TBPA) was used as a reactive chemical agent to prepare an esterified wood with the high dimensional stability, flame resistance, and resistance to biodegradation from water-leaching. The experimental results indicated that esterification of wood plus maleic anhydride / tetrabromophthalic anhydride / glycerol could endow wood with dimensional stability, the antiswelling efficiency during water absorption (ASEw), reduction in water absorptivity (RWA), antiswelling efficiency during moisture absorption (ASEm),moisture excluding efficiency (MEE), and oxygen index (OI) of treated wood increased with an increase in the weight percent gain(WPG). And the treated wood showed great decay resistance and resistance to water leaching, too.