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.     

Modification of wood with silicon compounds. Treatment systems based on organic silicon compounds — a review

A wide variety of organo-silicon compounds has been described for application on wood. Some compounds such as organo-functional silanes which are mostly applied in combination with tetraalkoxysilanes (sol-gel process) as well as chlorosilanes and trimethylsilyl derivatives were proposed for a full impregnation treatment of wood. Other systems have been developed for surface treatment of wood such as plasma coating with hexametyldisiloxane and micro-emulsions which mainly contain silane/siloxane mixtures. The effects related to the various treatments vary from an increase in dimensional stability, durability and fire resistance to an enhanced hydrophobation of wood. In the cases of decay and fire resistance a combination of silicon based systems with other chemicals was required to obtain satisfactory results. Due to the excellent water repellent ability and weathering stability of some treatments, application of silicon treated wood under conditions of hazard class III (EN 335 outside above ground exposure) is recommended.Abbreviations ASE anti-shrink efficiency - ATR-FT-IR attenuated total reflectance — Fourier transform infrared spectroscopy - CP MAS-NMR cross polarisation magic angle spinning nuclear magnetic resonance spectroscopy - DTA differential thermal analysis - DTMOS decyltrimethoxysilane - EDX energy dispersive x-ray analysis - EETMOS -(3,4 epoxycyclohexyl) ethyl trimethoxysilane - EMC equilibrium moisture content - ESCA electron spectroscopy for chemical analysis - HFOETMOS 2-heptadecafluorooctylethyltrimethoxysilane - HMDSO hexamethyldisiloxane - IPTEOS 3-isocyanatepropyl triethoxysilane - MPTMOS -methacryloxypropyl trimethoxysilane - MTMOS methyltrimethoxysilane - PDMS polydimethylsiloxane - PTMOS propyltrimethoxysilane - TEOS tetraethoxysilane / triethyl orthosilicate - TFPTMOS 3,3,3-trifluoropropyltrimethoxysilane - TGA thermo-gravimetric analysis - TMSAH 3-(trimethoxysilyl)propyl (carboxymethyl) decylmethyl ammonium hydroxide inner salt - TMSCl trimethylsilyl chloride - TPT tetraisopropyl titanate - VTMOS vinyl trimethoxysilane - WPG weight percent gain - WRE water repellent efficiency     

PEG bulking of wood cell walls as affected by moisture content and nature of solvent

Movement of polyethylene glycol (PEG) 1000 from wood cell lumens into adjacent cell walls was studied for different cell wall moisture contents (MCs) and PEG solvents; relative amounts of PEG that penetrated into the cell walls were estimated by Raman microscopy. It was shown that samples treated with PEG from chloroform solution adsorb less PEG than samples treated with PEG-water solution even in the case of samples with open cell wall structure near fibre saturation point MC. Reconditioning of PEG-chloroform treated samples at high relative humidities enhanced PEG bulking of cell walls, but not to the maximum amounts observed with PEG-water treatments. Raman microscopy was a useful tool for estimating relative PEG amounts in the cell walls.     

Effects of previous solvent exchange on acetylation of wood

Wood specimens were prepared in a swollen state using solvent exchange (PS) treatment. The swollen wood specimens were acetylated using acetic anhydride by heating at 80–120°C. At the beginning of heating, the weight percent gain (WPG) of PS-treated wood was greater than that of conventionally acetylated wood. This acceleration effect of the PS treatment was explained by the introduction of treating reagent into the wood polymers where the intermolecular hydrogen bonds were previously broken. On the other hand, the PS treatment had no influence on the final WPG and moisture sorption characteristics of acetylated wood. This indicated that the intrinsic reactivity of wood constituents was unaffected by the PS treatment. The acetylation of PS-treated wood produced greater bulking and slightly higher dimensional stability than that in the case of conventional acetylation at the same WPG. It was speculated that the expansion of cell lumina due to the PS treatment resulted in greater bulking on acetylation and lesser swelling of acetylated wood with moisture sorption.     

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.     

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     

Ultraviolet resistance and other physical properties of softwood polymer nanocomposites reinforced with ZnO nanoparticles and nanoclay

Wood polymer nanocomposites (WPNCs) based on nano-ZnO and nanoclay were prepared by impregnation of melamine formaldehyde–furfuryl alcohol copolymer, 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU), a cross-linking agent and a renewable polymer obtained as a gum from the plant Moringa oleifera under vacuum condition. Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometry (XRD) studies were employed for the characterization of modified ZnO and WPNCs. The change in crystallinity index (CrI) value of the cellulose in wood and the distribution of ZnO nanoparticles in composites were determined using FTIR and XRD. Scanning electron microscopy and Transmission electron microscopy showed the presence of nanoparticles and nanoclay in the cell lumen or cell wall of wood. An enhanced UV resistance property was shown by the treated wood samples as judged by lower weight loss, carbonyl index, lignin index, cellulose CrI values, and mechanical property loss compared to the untreated wood samples. Wood polymer composites treated with 3 phr each of nanoclay, ZnO, and the plant gum showed an improvement in mechanical properties, flame-retarding properties, thermal stability, and lower water uptake capacity.     

Modification of three hardwoods with an N-methylol melamine compound and a metal-complex dye

This study evaluated the combined modification and staining of ash, beech and maple wood with a low molecular weight N-methylol melamine compound (NMM) and a metal-complex dye. Wood samples were treated with aqueous solutions of 10, 20 and 30 wt% NMM and 5 wt% of the dye. The treatment caused the fixation of the water-soluble dye by the NMM resin. Vacuum pressure impregnation of unsealed wood blocks did not result in different solution uptake and weight percent gain after curing among the three species, but sealing of the surfaces of the wood blocks to allow penetration only into one direction revealed easiest penetrability of beech followed by maple and ash. UV micro-spectrophotometry and light microscopy indicated that NMM was partly deposited in the cell wall and partly in the lumens. Penetration of the metal-complex dye was shown by means of X-ray micro-analysis (SEM–EDX). The study shows that a combined resin modification and staining of the three wood species tested is possible and that NMM causes fixation of the water-soluble dye.     

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.     

Characteristics of fast-growing wood impregnated with nanoparticles

Falcataria moluccana or sengon is one of the fast-growing wood species widely grown in Indonesia.However,its wood is low quality with low density,and poor strength,durability,and dimensional stability.This study determined the effects of impregnation with monoethylene glycol(MEG)and nano-SiO2 on the characteristics of sengon wood,including its dimensional stability and density.Impregnation with MEG and nano-SiO2 had a significant effects on dimensional stability in terms of the weight percent gain,anti-swelling efficiency,water uptake,bulking effect,and density.The impregnated wood was examined by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray diffraction.The results show that MEG and nano-SiO2 were distributed homogeneously into cell walls of wood treated with 0.5%MEGSiO2.     

Improvement of mechanical properties of thermally modified hardwood through melamine treatment

Specimens of beech, ash, lime and poplar were thermally modified (T) and treated with an aqueous solution of melamine (M) resin to investigate the mechanical changes after combined (double) modification (TM). Density, solution uptake, weight percent gain, bulking and equilibrium moisture content were recorded to ensure proper treatment. Samples for Brinell hardness and three-point bending were cured at 120°C under dry conditions. The WPGs of the two treatment groups M and TM were similar, but bulking of TM specimens was negative. This might indicate an incomplete penetration into the thermally modified cell wall in combination with a potential leaching of soluble hemicellulose components by the alkaline impregnation solution. The decreased hardness of heat-treated wood was substantially increased by melamine treatment (combined modification). Both modifications and their combination slightly increased the modulus of elasticity. The modulus of rupture was increased after melamine treatment, decreased after thermal modification and combined modification. The work in bending was severely reduced for all treatments. Melamine treatment of thermally modified wood was carried out successfully and some mechanical properties were improved. Double-modified wood with increased modulus of rupture (MOR) and extraordinary surface hardness would be suitable for non-structural outdoor applications such as decking and cladding.

Abbreviations: ANOVA: Analysis of variance; EMC: Equilibrium moisture content; EMC_R: Reduced (corrected) equilibrium moisture content; IB: Impact bending strength; M: Melamine treated; MOE: Modulus of elasticity; MOR: Modulus of rupture; MUF: melamine-urea-formaldehyde resin; OD: Oven dry density; R: Untreated references; RH: relative humidity; SC: Solid content; SU: Solution uptake; T: Thermally modified; TM: Thermally modified and melamine treated (double modification); WB: Work in bending; WPG: Weight percent gain     

Chemical modification of wood by non-formaldehyde cross-linking reagents

Summary The probability of bond between wood components and glyoxal was examined by means of a mechanical method, infrared (IR) spectrometry, and solid state ¹³C-nuclear magnetic resonance (NMR) spectrometry. The successive fixation of a compressed wood by the glyoxal treatment suggested the formation of cross-linkings between wood components and/or wood structures. The IR spectra showed that ester bond as well as ether bond was formed between wood components and glyoxal. The existence of linkages between glyoxal and cellulose was indicated also from the NMR spectra. The addition of glycol to the glyoxal solution was investigated from the viewpoint of stabilizing effect of the linkages. When 0.2 mole ratio of glycol was added to 5–10% glyoxal solution, weight gain and antiswelling efficiency (ASE) were largest, however the addition of excessive amount of glycol did not advance further the weight gain and ASE. When an appropriate amount of glycol was added to the impregnation solution, both weight and ASE did not largely reduce even by the repeated hot water soaking. By the treatment without glycol, the dimensional stability after water soaking was attributed to only restraint of the swelling. On the other hand, when the glycol was added, the dimensional stability was developed not only by the restraint of the swelling but also by the buckling effect.We would like to thank Associate Professor Dr. Umezawa, Wood Research Institute, Kyoto University, for his invaluable support in NMR analysis. Thanks are also due to Dr. Inoue, Wood Research Institute, Kyoto University, for his preparing the wood specimens.     

Dimensional stability of wood acetylated with acetic anhydride solution of glucose pentaacetate

Five wood species were acetylated with acetic anhydride (AA) solution of glucose pentaacetate (GPA) at 120°C for 8h, and the effect of GPA on the dimensional stability of the acetylated wood was investigated. Some GPA was introduced into the wood cell wall during acetylation. The GPA remaining in the cell lumen penetrated the cell wall effectively after heating to more than 140°C for 10min. The bulking effects of GPA resulted in a 10%–30% increase in the anti-swelling efficiency of the acetylated wood with 20% GPA/AA solution in place of AA. Hydrophobic GPA did not deliquesce under highly humid conditions and it remained in the cell wall after boiling in water.Part of this paper was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 1988     

Effects of impregnation and heat treatment on the physical and mechanical properties of Scots pine (Pinus sylvestris) wood

Wood modification, of which thermal modification is one of the best-known methods, offers possible improvement in wood properties without imposing undue strain on the environment. This study investigates improvement of the properties of heat-treated solid wood. Scots pine (Pinus sylvestris) was modified in two stages: impregnation with modifiers followed by heat treatment at different temperatures. The impregnation was done with water glass, melamine, silicone, and tall oil. The heat treatment was performed at the temperatures of 180°C and 212°C for three hours. The modified samples were analyzed using performance indicators and scanning electron microscope micrographs. The mechanical and physical properties were determined with water absorption, swelling, bending strength, and impact strength tests. All the modifiers penetrated better into sapwood than hardwood; however, there were significant differences in the impregnation behavior of the modifiers. As regards the effect of heat treatment, generally the moisture properties were improved and mechanical strengths impaired with increasing treatment temperature. In contrast to previous studies, the bending strength increased after melamine impregnation and mild heat treatment. It is concluded that the properties of impregnated wood can be enhanced by moderate heat treatment.     

甘油预处理对热处理材尺寸稳定性的影响

为提高木材的尺寸稳定性,采用甘油水溶液对毛白杨和云杉进行预处理,然后再进行热处理.通过检测处理材的密度、平衡含水率、吸水和吸湿抗胀率等,结果表明:与未预处理的热处理材相比,经甘油水溶液预处理后,热处理材的密度增加率提高;平衡含水率先降低后增加;吸水和吸湿抗胀率均显著增加.     

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。     

Improvement of wood properties by composite of diatomite and “phenol-melamine-formaldehyde” co-condensed resin

We improved the overall performance of fast-growing poplar by utilizing a low-cost, effective and simple method. The fast-growing poplar was modified by a vacuum-pressure impregnation method with three...     

Effects of borate impregnation on the response of wood strength to heat treatment

Based on the strong correlation between acidity and thermal degradation in wood reported in previous studies, the effect of borate impregnation as an alkali-buffering medium was investigated on the strength properties of thermally modified wood. Wood samples were impregnated with 0.1 M Sodium borate solution (pH=9) before they were subjected to heat treatment at temperatures of 180°C and 200°C for durations of 2 and 4 h. The borate impregnation results in some reductions in the severity of strength loss during heat treatment and this is invariably due to buffering effect of the alkali on the acidity of wood, which could have mitigated the degree of degradation. The positive effects of borate impregnation as a pretreatment on the strength properties of heat-treated wood depend on the degree of heat treatment. Hence, the use of borate impregnation as a pretreatment method for heat treatment is recommended only where a relatively mild heat treatment is involved.     

Structure and characterization of Chinese fir (Cunninghamia lanceolata) wood/MMT intercalation nanocomposite (WMNC)

With water-soluble phenol-formaldehyde resin as an intermediate, Chinese fir (Cunninghamia lanceolata) wood/montmorillonite nanocomposite (WMNC) was prepared through vacuum impregnation and characterized with XRD, SEM, FTIR and TG-DTA analyses. The XRD analysis indicated that the wood crystallinity of WMNC decreased, the MMT exfoliated and some nano silicate layers entered into the non-crystallized microfibrillar region of the wood cell wall. Wood structure is anisotropic and its impregnation is anisotropic. Due to the nonuniformity of the MMT organic modification, PF intercalation and wood impregnation, the MMT configuration and distribution in wood were diverse. The SEM graphs of WMNC showed that some silicate grains were blocked in the wood cell lumen, some silicate layers adhered to the inner surface of the wood cell wall, and some exfoliated MMT layers even penetrated the wood cell wall. The obtained hydroxyl of WMNC increased and its ether linking decreased. It was considered that MMT and wood interacted not only with hydroxyl bonds, but also involved some chemical linking. Compared with untreated wood and the PF-impreg, the pyrolysis process of WMNC changed; its starting decomposing temperature decreased and its pyrolysis weight loss at high temperatures greatly decreased. The WMNC indicated certain nanoeffects of the composition of the inorganic MMT nanolamellae. __________ Translated from Journal of Beijing Forestry University, 2007, 29(1): 131–135 [译自: 北京林业大学学报]     

Effect of nanofillers on flame retardancy, chemical resistance, antibacterial properties and biodegradation of wood/styrene acrylonitrile co-polymer composites

Wood polymer nanocomposites (WPNCs) based on simul wood (Bombex ceiba, L.) were prepared by impregnation of styrene acrylonitrile copolymer, γ-methacryloyloxy trimethyl silane-modified TiO₂, SiO₂ nanoparticles and nanoclay intercalating mixture through vacuum impregnation. The impact of nanofillers on the physical properties, flame retardancy, water resistance, anti-swelling efficiency and biodegradability of the resultant WPNCs was investigated. Remarkable enhancement in wood properties such as flame retardancy, water resistance and anti-swelling efficiency was achieved with the treatment. The results showed that all the properties were maximum for wood samples treated with SAN/TiO₂ (0.5 %)/SiO₂ (0.5 %)/nanoclay (0.5 %). The presence of TiO₂ nanoparticles in WPNC exhibited antibacterial activity. The resistance to biodegradation was observed by incorporation of nanofillers into wood.