Potassium acetate-catalyzed acetylation of wood at low temperatures I: simplified method using a mixed reagent

Ezomatsu wood blocks were acetylated in a mixture of acetic anhydride and acetic acid containing excess potassium acetate (KAc). The mixture method enabled rapid acetylation at 120°C: a 20% weight gain (weight percent gain; WPG) was achieved within 30 min while the WPG did not exceed 18% after 120 min of conventional uncatalyzed acetylation. At 40°C, however, a satisfactory WPG was not achieved with the mixture method because both the wood swelling and KAc concentration in the reagent solution were limited at that temperature. In addition, the antiswelling efficiency attained by the mixture method was irregularly low, probably because of nonuniform reaction involving shrinkage of the cell lumina. These results suggest that the mixture method is not advantageous for low-temperature acetylation, whereas it enables simple and rapid acetylation at high temperature.     

Potassium acetate-catalyzed acetylation of wood: reaction rates at low temperatures

Spruce wood blocks were acetylated in the presence of potassium acetate (KAc) at 20, 40, 60, 80 and 120°C. At 20°C, the weight percent gain (WPG) due to the KAc-catalyzed acetylation reached 20% in 18 days, whereas that due to pyridine-catalyzed acetylation did not exceed 8%. The hygroscopicity and dimensional stability of the KAc-acetylated wood were the same as those of conventionally acetylated wood at the same WPG, irrespective of reaction temperature. These facts suggest that the KAc enables simplified acetylation of wood at room temperature. The activation energy (E _a) of the KAc-acetylation in the lower temperature range (20–40°C, 121–131 kJ/mol) was comparable to that of the acetylation of wood meal (140–146 kJ/mol). It was speculated that diffusion became a minor factor at reduced reaction rates in the lower temperature range, thus requiring a greater E _a.     

Dependence of reaction kinetics and physical and mechanical properties on the reaction systems of acetylation II: physical and mechanical properties

Acetylation of wood was carried out in acetic anhydride only, acetic anhydride/xylene 1:1 (v/v), and acetic anhydride/pyridine 4:1 (v/v) solutions. The antishrink efficiency (ASE), hygroscopic properties, vibrational properties, and bending strength were compared among the three reaction solutions. The ASE was a simple function of weight gain (WG); the equilibrium moisture content at a given WG differed among the reaction solutions. Based on this fact and the results of repeated water soaking and oven-drying tests, it was found that the bulking effect was a major factor, and that decreased hygroscopicity contributes only slightly to the dimensional stabilization by acetylation. The difference in equilibrium moisture content among reaction solutions appears more significant in block samples than wood meal, probably due to the fiber-to-fiber bonds in the former. The tendencies for change in the specific Youngs modulus and the loss tangent differed among reaction solutions, whereas in the static bending test the difference was not marked.Part of this report was represented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

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     

Vapor phase reaction of wood with maleic anhydride (II): mechanism of dimensional stabilization

The vapor phase reaction of wood with maleic anhydride (MA) was investigated from the aspect of the mechanism of dimensional stabilization. Notably the existence of cross-links was examined by detailed analyses of dimensional stability and related properties, diffuse reflectance infrared Fourier transform (DRIFT) spectra, and changes in mechanical properties such as creep property and vibrational property. Higher reaction temperature resulted in less leaching of reagent. Also a peak in DRIFT spectra at 1730 cm⁻¹ showed the esterification of wood components with MA, while that at around 1780 cm⁻¹, which became remarkable with increasing reaction temperature, suggested the formation of cross-linking. The loss tangent decreased and the creep deformation was restrained for the specimens treated at high temperature. From these results it is plausible that MA mainly forms monoester with wood components at lower temperature; however, at elevated temperature cross-linking appears in addition to formation of the monoester.     

Effects of low bondability of acetylated fibers on mechanical properties and dimensional stability of fiberboard

Fiberboards were prepared from acetylated fibers with various weight gains: 0, 4.7, 9.4, 18.5, and 24.8 weight percent gain (WPG). The effects of low bondability of acetylated fibers on mechanical properties and dimensional changes were determined. The decreased mechanical properties of acetylated fiberboard are mainly due to low bondability. To improve bending strength, high face density is also needed. The thickness swelling according to JIS and the linear expansion under relative humidity changes decreased with increasing WPG. As for accelerated weathering and the outdoor exposure test, the thickness changes in 4.7–18.5 WPG boards were much higher than those in OWPG board and 24.8 WPG board. The high thickness change in 4.7–18.5 WPG boards is due to low bondability. Although 24.8 WPG board also has low bondability, the thickness change of 24.8 WPG board decreased. The high dimensional stability of acetylated fibers, caused by high WPG, probably outweighs the dimensional change caused by low bondability. On the other hand, during the boiling test the thickness changes in 24.8 WPG board and the 4.7–18.5 WPG boards were higher than those in 0 WPG board. The effect of the boiling test on the boards is more severe than that seen with the accelerated weathering and outdoor exposure test; therefore, the effects of the low bondability probably cancel the effects of the high WPG. It is necessary to increase the bondability of acetylated fibers to improve the dimensional stability and the mechanical properties.     

Vapor phase reaction of wood with maleic anhydride (I): dimensional stability and durability of treated wood

Reaction between maleic anhydride (MA) and wood specimens was carried out in a vapor phase reaction system. Reaction conditions such as the ratio of supplied MA to wood, initial moisture content, and reaction temperature were optimized. The MA supplied to the reaction system was effectively absorbed by the wood, and a satisfactorily high dimensional stability was achieved even at a low MA/wood ratio. The dimensional stability increased with rising initial moisture content. When the reaction was conducted at an elevated temperature (180°C), high dimensional stability was attained without remarkable weight increase and bulking. The mechanism of dimensional stabilization was discussed on the basis of the dimensional changes at high humidity and during repeated water soaking and drying. It was shown that the dimensional stabilization arises mainly from a decrease of hygroscopicity. When the reaction was conducted at 180°C, the formation of cross-links in the cell wall was apparent. Following the MA treatment, the antifungal property was remarkably enhanced and met the Japanese Industrial Standard K1571. Therefore, MA treatment in the vapor phase is an effective method to attain antifungal properties as well as high dimensional stability with a small amount of nontoxic reagent.     

Swelling of acetylated wood II: effects of delignification on solvent adsorption of acetylated wood

To clarify the role of lignin in the affinities of acetylated wood for organic solvents, the effects of delignification on the solvent adsorption of acetylated wood were investigated. Acetylated wood meals rapidly adsorbed organic solvents that were hardly adsorbed by unmodified wood. For nonpolar and low-polarity organic solvents, a clear positive correlation was observed between the amount of adsorption and the lignin content. This indicated that acetylated lignin was responsible for the excellent affinities of acetylated wood for hydrophobic organic solvents. On the other hand, for lower alcohols and water, the amount of adsorption reduced with an increase in the lignin content. It was suggested that the adsorption of such polar solvents was dominated by insufficiently acetylated hydrophilic polysaccharides.     

木材液相乙酰化处理及处理材尺寸稳定性和耐腐性的研究

本文论述了马尾松、白桦和青杨三种木材的液相乙酰化条件及各种乙酰化木材的尺才稳定性和耐菌腐能力。以乙酸酐和二甲苯为处理液,反应的最佳条件是:温度120℃,时间7到11小时,乙酸酑与二甲苯配比1:1。当处理试样的增重到15%时,抗收缩率可达60%以上。增重为11.75—17.98%的不同处理试块,其耐菌腐能力可提高3—34倍。     

Contribution of lignin to the reactivity of wood in chemical modifications I: influence of delignification on acetylation

In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol. These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004     

Spectrochemical characterization by FT-Raman spectroscopy of wood heat-treated at low temperatures: Japanese larch and beech

Test samples of Japanese larch (Larix leptolepis) heartwood and Japanese beech (Fagus crenata) sapwood were heated for 22 h at constant temperatures (50°–180°C) under three water content conditions. Raman spectra of the samples were recorded before and after the heat treatments, and spectral changes in the range from 1000 cm⁻¹ to 1800 cm⁻¹ were evaluated using the difference spectrum method. For both wood species, the Raman band intensity at 1655–1660 cm⁻¹ due mainly to the C=C and C=O groups in lignin clearly decreased with increasing heat-treatment temperature (HTT). The spectral change was thought to reflect the progress of condensation reactions of lignin molecules during the heat treatment. Moreover, the decrease in band intensity was considerably facilitated by the presence of water in the cell wall, suggesting that the condensation is closely related to the softening of lignin. From the spectral changes in the wavenumber region of 1200–1500 cm⁻¹, it was considered that wood constituents are partially decomposed at the higher HTT. Part of this article was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, March 2003     

Optimization and simulation of drying processes using diffusion models: application to wood drying using forced air at low temperature

This paper discusses the suitability of four diffusion models to describe the drying of wood. The first model refers to the analytical solution of an infinite slab with boundary condition of the first kind. In the last three models, the boundary condition is of the third kind and the analytical solutions refer to the following geometries: infinite slab, rectangle, and parallelepiped. The analytical solutions were coupled to an optimizer based on inverse method, which enables to calculate process parameters for an experimental data set. Once the process parameters were determined, the drying kinetics of wood was simulated through each model proposed. The obtained results lead to the conclusion that the first model does not represent the drying kinetics properly. The last three models adequately describe the drying kinetics, but statistical indicators enable to affirm that the best of them is the three-dimensional model.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin II: effects of processing parameters

To obtain high-strength phenol formaldehyde (PF) resin-impregnated compressed wood at low pressing pressure, the effects of resin content, preheating temperature, pressing temperature, and pressing speed on the compressive deformation of oven-dried low molecular weight PF resin-impregnated wood was investigated. With an increase of PF resin content, the Youngs modulus of the cell wall perpendicular to the fiber direction decreases, and collapse-initiating pressure decreases linearly with the Youngs modulus. This indicates that the occurrence of cell wall collapse is strain-dependent. By increasing preheating temperatures, the collapse-initiating pressure increases due to the increment of the Youngs modulus of the cell wall. An increase in pressing temperature results in the thermal softening of the cell wall and causes collapse at a lower pressure. The wood is compressed effectively despite accelerated resin curing. The pressing speed significantly affects the viscoelastic deformation of the cell wall and the wood is well deformed with decreasing pressing speed, although the differences in density and mechanical properties are relatively small after a pressure-holding period of 30min. In all the parameters examined in this study, the Youngs modulus and bending strength increase with increasing density.     

Bondability of tropical fast-growing tree species III: curing behavior of resorcinol formaldehyde resin adhesive at room temperature and effects of extractives of <Emphasis Type="Italic">Acacia mangium</Emphasis> wood on bonding

The effects of curing time at room temperature and methanol extracts from Acacia mangium on the curing behavior of resorcinol formaldehyde (RF) adhesive were examined by using the thermomechanical analysis spring method. For a specimen that was cured for 3 months at room temperature, the relative elasticity (E _r) curve did not change to a hard glass state from room temperature to 200°C and the adhesive had cured completely. The initial temperature of the reactive zone for chemical and mechanical changes was 15° and 25°C higher than that for the control when 10 and 15 parts by weight methanol extract was added to the liquid adhesive, respectively. It appears that the extractives of A. mangium in RF adhesive interferes with the chemical cure of the adhesive. It is suggested that a combination of curing time and sweeping by methanol on the laminae surface can improve the bonding performance of A. mangium laminates bonded with RF at room temperature.     

Effects of high temperature kiln drying on the practical performances of Japanese cedar wood (Cryptomeria japonica) II: Changes in mechanical properties due to heating

Japanese cedar wood specimens were steamed at 80°, 100°, and 120°C over 14 days, and their equilibrium moisture content (M) at 20°C and 60% relative humidity, longitudinal dynamic Young’s modulus (E), bending strength (σ _max), and breaking strain (ε _max) were compared with those of unheated specimens. Steaming for a longer duration at a higher temperature resulted in a greater reduction in M, σ _max, and ε _max. The E of wood was slightly enhanced by steaming at 100°C for 1–4 days and 120°C for 1–2 days, and thereafter it decreased. The slight increase in the E of sapwood was attributable to the reduction in hygroscopicity, while sufficient explanation was not given for a greater increase in the heartwood stiffness. Irrespective of the steaming temperature, the correlations between M and the mechanical properties of steamed wood were expressed in terms of simple curves. M values above 8% indicated a slight reduction in E and s max, whereas M values below 8% indicated a marked decrease in the mechanical performances. In addition, the e max decreased almost linearly with a decrease in the value of M. These results suggest that hygroscopicity measurement enables the evaluation of degradation in the mechanical performances of wood caused by steaming at high temperatures.     

Stress relaxation of wood during elevating and lowering processes of temperature and the set after relaxation II: consideration of the mechanism and simulation of stress relaxation behavior using a viscoelastic model

Previously we showed that the relaxation modulusEt of water-saturated wood during temperature reduction maintained its initial value despite the decrease in temperature, although during temperature elevationEt showed a marked decrease. In the present study, to clarify the mechanism of relaxation during temperature elevation and reduction, Young's modulus was measured in stress relaxation experiments with changes in temperature, and relaxation behavior was simulated using a Maxwell model consisting of five elements. Furthermore, the dynamic Young's modulus and dynamic loss modulus were measured during both temperature elevation and reduction. The results obtained suggested that the unique relaxation behavior during temperature reduction was caused by decreases in Young's modulus and coefficient of viscosity (i.e., an increase in fluidity) compared with those during elevation of temperature. The decrease in Young's modulus and increase in fluidity were considered to be due to an unstable structure in wood that occurred during temperature reduction. This unstable structure probably develops in the nonequilibrium state of temperature toward a true equilibrium state. Wood should be more unstable during temperature reduction than during temperature elevation because of the decrease in molecular motion when the temperature is lowered.Part of this report was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999     

Effect of bamboo vinegar on regulation of germination and radicle growth of seed plants II: composition of moso bamboo vinegar at different collection temperature and its effects

Moso bamboo vinegar was treated with extractive and separation methods. The acidic, neutral, and phenolic fractions separated from ether-extracted vinegar were analyzed by gas chromatography and gas chromatography-mass spectrometry to identify the major components in moso bamboo vinegar. The compositions of eight moso vinegar fractions collected over different temperature ranges from 100°C to 480°C were also analyzed and their effects on regulation of germination and growth were studied by bioassay with seeds of watercress and chrysanthemum. The results showed that moso bamboo vinegar fractions with collection temperatures up to 250°C promoted radicle and hypocotyl growth and this effect became larger with increasing collection temperature for chrysanthemum. Moso bamboo vinegar collected from 250°C to 400°C had a strong inhibition on germination and radicle growth for both seed types when tested at 10³ dilution.