Green color protection of bamboo culms using one-step alkali pretreatment-free process

This study evaluated the protection effectiveness of alcohol-borne reagents for the green color of ma bamboo (Dendrocalamus latiflorus Munro) and moso bamboo (Phyllostachys pubescens Mazel). The results show that the types and concentrations of alcohol-borne reagents, the kinds of solvent, and the conditions of treatment greatly affected the green color of these two bamboo species. Without alkali pretreatment, an excellent green color protection (a* = −14.5) was obtained when the ma bamboo culms were treated with 0.5% methanol-borne copper chloride (CuCl₂) at 60°C for 30 min. Similar results were also obtained when ma bamboo culms were treated with 0.5% methanol-borne copper nitrate [Cu(NO₃)₂] at 60°C for 2 h (a* = −13.5). For moso bamboo, an attractive green color in the bamboo culms was achieved by treating the specimens with 1% methanol-borne copper acetate [Cu(CH₃COO)₂] at 60°C for 30 min. The a* value of treated specimens was −13.3. In addition, results demonstrated that ultrasonic treatment was more effective on green color protection than conventional water bath treatment. When moso bamboo was treated with 1% copper acetate at 60°C in an ultrasonic bath for only 15 min, a remarkable green color with an a* value of −13.6 was obtained on the bamboo epidermis.     

Feasibility of supercritical carbon dioxide as a carrier solvent for preservative treatment of wood-based composites

 Supercritical carbon dioxide (SC-CO₂) was tested for its potential as a carrier solvent for preservative treatment of solid wood and wood-based composites. A preliminary trial showed that the treatability of solid wood varied with its original permeability and that the SC-CO₂ treatment was not promising for refractory timber species such a Larix leptolepis Gordon. In contrast, 3-iodo-2-propynyl butylcarbamate (IPBC)/SC-CO₂ treatment resulted in enhanced decay resistance without any detrimental physical or cosmetic damage in all structural-use wood-based composites tested: medium density fiberboard, hardwood plywood, softwood plywood, particleboard, and oriented strand board (OSB). Further trials under various treatment conditions [25°C/7.85 MPa (80 kgf/cm²), 35°C/7.85 MPa, 45°C/7.85 MPa, 35°C/11.77 MPa (120 kgf/cm²), and 45°C/11.77 MPa] indicated that although small changes in the weight and thickness of the treated materials were noted the strength properties were not adversely affected, except for a few cases of softwood plywood and oriented strand board. The results of this study clearly indicated that the treatment condition allowed SC-CO₂ to transport IPBC into wood-based composites, and the optimum treatment condition seemed to vary with the type of wood-based composite. Received: October 24, 2001 / Accepted: February 15, 2002 Part of this work was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001; and the 32nd Annual Meeting of the International Research Group on Wood Preservation, Nara, May 2001 Correspondence to:M. Muin     

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     

Experimental determination of the convective heat and mass transfer coefficients for wood drying

The knowledge of the convective heat and mass transfer coefficients is required for the characterization of the boundary conditions of the heat and mass transfer equations of a wood drying model based on water potential. A new experimental method for the determination of the convective mass transfer coefficient is presented. This method is based on the measurement of the moisture content, and indirectly the water potential, at the surface of a wood specimen at different drying times. Drying experiments were performed on red pine (Pinus resinosa Ait.) sapwood from nearly saturated to dry conditions at 56 °C, 52% relative humidity and air velocities of 1.0, 2.5 and 5.0 m s⁻¹. The results show that the convective mass transfer coefficient is constant until the wood surface moisture content reaches about 80% and then decreases more or less gradually as the moisture content decreases further. The convective mass transfer coefficient increases with air velocity. A regression analysis shows that there is no significant improvement in considering the water potential gradient near the wood surface when the difference in water potential between the surface and the surrounding air (ψ_s − ψ_∞) is used to determine the convective mass flux at the surface. Also, ψ_s − ψ_∞ is more appropriate than the water vapour pressure difference (pv_s − pv_∞) as the responsible driving force of the moisture flux leaving the wood surface. The convective heat transfer coefficient was determined during the same experiments. A plateau is observed at high values of moisture content corresponding to the constant drying rate period. Received 27 February 1998     

Dynamic viscoelastic properties of wood acetylated with acetic anhydride solution of glucose pentaacetate

 Spruce wood specimens were acetylated with acetic anhydride (AA) solutions of glucose pentaacetate (GPA), and their viscoelastic properties along the radial direction were compared to those of the untreated and the normally acetylated specimens at various relative humidities and temperatures. Higher concentrations of the GPA/AA solution resulted in more swelling of wood when GPA was introducted into the wood cell wall. At room temperature the dynamic Young's modulus (E′) of the acetylated wood was enhanced by 10% with the introduction of GPA, whereas its mechanical loss tangent (tan δ) remained almost unchanged. These changes were interpreted to be an antiplasticizing effect of the bulky GPA molecules in the wood cell wall. On heating in the absence of moisture, the GPA-acetylated wood exhibited a marked drop in E′ and a clear tan δ peak above 150°C, whereas the E′ and tan δ of the untreated wood were relatively stable up to 200°C. The tan δ peak of the GPA-acetylated wood shifted to lower temperatures with increasing GPA content, and there was no tan δ peak due to the melting of GPA itself. Thus the marked thermal softening of the GPA-acetylated wood was attributed to the softening of wood components plasticized with GPA. Received: March 29, 2002 / Accepted: May 21, 2002 Correspondence to:E. Obataya     

Real-time measurement of vibrational properties and fine structural properties of wood at high temperature

Vibrational properties and fine structural properties of wood were measured at high temperatures. Sitka spruce (Picea sitchensis Carr.) and Shioji (Japanese ash, Fraxinus spaethiana Lingelsh.) were used as specimens. The specimens, the system to support them, a magnetic driver, and a deflection sensor were in an electric drying oven, where vibration tests were conducted. The heating temperatures ranged from room temperature to 200 °C in 25 °C increments in both heating and cooling processes. X-ray diffractometry was carried out using positive sensitive proportional counter (PSPC) at room temperature to 200 °C in 20 °C increments in both heating and cooling processes. Received 13 December 1999     

Extraction and decomposition of hiba wood into valuable chemicals using stepwise temperature supercritical carbon dioxide treatment

Hiba (Thujopsis dolabrata) wood was treated with supercritical carbon dioxide (scCO₂) at stepwise temperature increments from 50° to 400°C continuously so that extractives (dichloromethane-soluble and -insoluble phases) and solid residues were obtained. The yield of extractives from hiba wood increased with increasing extraction temperature. The volatile compounds in the dichloromethane-soluble phase from scCO₂ extraction at 50°C contained only terpenoids. However, the volatile compounds in the dichloromethane-soluble phase from scCO₂ extraction at 300°C not only contained terpenoids but also phenols, furans, hydrocarbons, and organic acids. The yield of β-thujaplicin, which is a useful compound in hiba wood, increased with increasing extraction temperature from 50°C to 300°C; the optimal conditions for extracting β-thujaplicin were 300°C and 19.61 MPa. Further study of degradated compounds from the cellulosic and lignic materials of hiba wood after stepwise high-temperature scCO₂ treatment above 300°C may provide clues to its efficient use.     

Chemical kinetics of Japanese cedar,cypress, fir,and spruce and characterization of charcoal

 Thermogravimetric and differential thermal analyses techniques have been applied to investigate the thermal degradation characteristics and chemical kinetics of Japanese cedar, cypress, fir, and spruce. The decomposition of the components could be modeled by an Arrhenius kinetic expression. The kinetic parameters were extracted from the thermogravimetric data using least-squares techniques. The heating rates used for the analyses were 10°, 5°, and 0.33°C/min; and the activation energy and reaction order of the above woods were 7.54, 8.39, 2.87, and 7.88 kJ/mol and 0.71, 0.64, 0.44, and 0.63, respectively. Finally, carbonization was done to produce charcoal from these woods under various operating conditions, and the charcoal was characterized in respect to yield, heating value, electrical conductivity, and X-ray diffraction. The quality of the charcoal from fir was the best among the four types of wood. The charcoal produced is inferior to binchotan (white charcoal) in respect to electrical conductivity and crystalline structure. Received: February 13, 2002 / Accepted: July 12, 2002 Acknowledgment The authors express their gratitude to Professor Yoshida of Applied Chemistry in Tokyo Metropolitan University for performing the TG/DTA in his laboratory and for his valuable suggestions about the analyses.     

Pyrolytic characteristics of burning residue of fire-retardant wood

In order to investigate the pyrolytic characteristics of the burning residue of fire-retardant wood, a multifunctional fire-resistance test oven aimed at simulating the course of a fire was used to burn fire-retardant wood and untreated wood. Samples at different distances from the combustion surface were obtained and a thermogravimetric analysis (TG) was applied to test the prrolytic process of the burning residue in an atmosphere of nitrogen. The results showed that: 1) there was little difference between fire-retardant wood and its residue in the initial temperature of thermal degradation. The initial temperature of thermal degradation of the combustion layer in untreated wood was higher than that in the no burning wood sample; 2) the temperature of the flame retardant in fire-retardant wood was 200°C in the differential thermogravimetry (DTG). The peak belonging to the flame retardant tended to dissipate during the time of burning; 3) for the burning residue of fire-retardant wood, the peak belonging to hemicellulose near 230°C in the DTG disappeared and there was a gentle shoulder from 210 to 240°C; 4) the temperature of the main peaks of the fire-retardant wood and its burning residue in DTG was 100°C lower than that of the untreated wood and its burning residue. The rate of weight loss also decreased sharply; 5) the residual weight of fire-retardant wood at 600°C clearly increased compared with that of untreated wood. Residual weight of the burning residue increased markedly as the heating temperature increased when burning; 6) there was a considerable difference with respect to the thermal degradation temperature of the no burning sample and the burning residue between fire-retardant wood and untreated wood. __________ Translated from Journal of Beijing Forestry University, 2006, 28(3): 133–138 [译自: 北京林业大学学报]     

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     

High-temperature mechanical properties and thermal recovery of balsa wood

This article presents an experimental study into thermal softening and thermal recovery of the compression strength properties of structural balsa wood (Ochroma pyramidale). Balsa is a core material used in sandwich composite structures for applications where fire is an ever-present risk, such as ships and buildings. This article investigates the thermal softening response of balsa with increasing temperature, and the thermal recovery behavior when softened balsa is cooled following heating. Exposure to elevated temperatures was limited to a short time (15 min), representative of a fire or postfire scenario. The compression strength of balsa decreased progressively with increasing temperature from 20° to 250°C. The degradation rates in the strength properties over this temperature range were similar in the axial and radial directions of the balsa grains. Thermogravimetric analysis revealed only small mass losses (<2%) in this temperature range. Environmental scanning electron microscopy showed minor physical changes to the wood grain structure from 190° to 250°C, with holes beginning to form in the cell wall at 250°C. The reduction in compression properties is attributed mostly to thermal viscous softening of the hemicellulose and lignin in the cell walls. Post-heating tests revealed that thermal softening up to 250°C is fully reversible when balsa is cooled to room temperature. When balsa is heated to 250°C or higher, the post-heating strength properties are reduced significantly by decomposition processes of all wood constituents, which irreversibly degrade the wood microstructure. This study revealed that the balsa core in sandwich composite structures must remain below 200°–250°C when exposed to fire to avoid permanent heat damage.     

Durability of thermally modified Norway spruce and Scots pine in above-ground conditions

Abstract

One of the main objectives of thermal modification is to increase the biological durability of wood. In this study the fungal resistance of Norway spruce and Scots pine, thermally modified at 195°C and 210°C, was studied with a lap-joint field test. Untreated pine and spruce and pine impregnated with tributyl tin oxide (TBTO) and copper, chromium and arsenic (CCA) were selected as reference materials. The evaluations were carried out after 1, 2 and 9 years of exposure. After 1 and 2 years of exposure mainly discoloration was detected. Only the untreated pine was slightly affected by decay fungi. There were significant differences in the decay ratings of untreated and thermally modified wood materials after 9 years in the field. While the untreated wood materials were severely attacked by decay fungi or reached failure rating, only small areas of incipient decay were detected in the thermally modified samples. Thermally modified pine was slightly more decayed than thermally modified spruce. The only wood material without any signs of decay was CCA-treated pine, since some of the TBTO-treated pine samples were also moderately attacked by fungal decay. The results of the lap-joint test had a good correlation with mass losses in a laboratory test with brown-rot fungi.     

Dielectric relaxation due to the heterogeneous structure of wood charcoal

Delignified hinoki wood and cellulose as well as hinoki and lauan woods were carbonized at 590°C for 1 h. The dielectric properties of these specimens were measured at 20°C in a frequency range of 20 Hz to 1 MHz. Inflection points in the dielectric constant (ε′) versus the logarithm of frequency (log f) curves as well as in the logarithm of the electric conductivity (log σ) versus log f curves for all specimens prepared were recognized. Peaks in the dielectric loss and the imaginary part of the complex conductivity versus the log f curves were detected in the frequency location corresponding to the inflection point in the ε′ and log σ versus log f curves. It was considered that this relaxation was responsible for the interfacial polarization observed in heterogeneous materials because no permanent dipoles existed in the specimens carbonized above 500°C. The Cole–Cole circular arc law was applied to account for this relaxation. Similar average relaxation times were obtained for all specimens. These results suggested that the observed relaxation was ascribed to interfacial polarization at microscopic levels in the cell walls.     

Characteristics of thermal decomposition of bamboo with different chemical additives

By means of the analysis of TG-DSC curves, we studied the effect of temperature and several additives, i.e., H₂SO₄, HCl, NaOH, H₂O₂ and H₃PO₄ on the performance of the thermal decomposition of bamboo. The results indicated that the weightlessness of pure bamboo powder may be divided into three stages, up to 700°C. At each stage, the effect of each chemical additive on the weightlessness rate of bamboo was different. In the end, we analyzed the function of additives in practical applications of the thermal decomposition of bamboo. __________ Translated from Journal of Bamboo Research, 2007, 26(1): 42–45 [译自: 竹子研究汇刊]     

Thermal-death kinetics of the bark beetle (Dendroctonus armandi; Coleoptera: Scolytidae)

Data on thermal-death kinetics of bark beetles are essential to develop phytosanitary heat treatments for pine wood and pine wood packaging materials. Using a heating block system, effects of different heating rates between 44 and 50°C at 2°C intervals on destruction of Dendroctonus armandi adult insect were examined. Heat resistance of the insects was found to increase at low heating rates (0.1 or 0.5°C/min). Therefore, the thermal-death kinetics of the beetles were determined at a high heating rate of 5.0°C/min which simulated the rapid dielectric heating of wood products. Results showed that the thermal death curve of D. armandi followed a zero-order reaction kinetic model, indicating the heat destruction rate of the beetle at different treatment temperatures to be independent of their population size. The required thermal holding times to result in destruction of the entire population were 40, 8, 4, and 2?min at 44°C, 46°C, 48°C, and 50°C, respectively. The evaluated thermal-death kinetic data are useful in developing effective beetle elimination quarantine protocols for the wood. A 50°C ?2?min heat treatment with a heating rate of ～5°C/min can be effectively used for disinfesting bark wood materials.     

Raman spectroscopic study on the behavior of boric acid in wood

 Raman spectra of Japanese cedar (Cryptomeria japonica D. Don) treated by vacuum impregnation with aqueous boric acid solutions (8.1 × 10⁻² to 7.29 × 10⁻¹ mol dm⁻³) were recorded using a near-infrared laser as an excitation source. Raman spectroscopic measurements were carried out on treated wood blocks of two sizes: 20(T) × 20(R) × 5(L) mm (A-type) and 15(T) × 15(R) × 50(L) mm (B-type). Our attention was focused on a prominent band (ν ₁) assigned to a symmetrical stretching vibration of the BO₃ group because no Raman band due to boron species was observed except bands of B(OH)₃. We observed a change in ν ₁ band intensity with increasing boric acid concentration in the aqueous solution used to treat the A-type wood blocks and investigated the correlation between the intensity and the peak-top wavenumber. Raman line maps in the longitudinal direction of the treated B-type wood blocks revealed that B(OH)₃ is concentrated near the cut ends. These results suggested that two groups of B(OH)₃ exist in wood in terms of the chemical species in the nearest neighbor sphere. Received: March 11, 2002 / Accepted: June 26, 2002     

The effects of wood species and treatment retention on kinetics of CCA-C fixation reactions

Reaction kinetics of fixation of CCA-C (chromated copper arsenate type C) preservative was studied at 30°C in ground wood of trembling aspen, red pine, and red maple at treatment retentions of 4.0, 6.4, 9.6, and 30 kg/m³, and red maple pre-extracted with hot water at retentions of 6.4 and 30 kg/m³. Reaction orders of cumulative Cr, Cu, and As reactions decreased gradually during the fixation if calculated by Van’t Hoff’s method. With Essen’s method, CCA fixation was best approximated as follows: Cr—3rd order reaction during the first 24 h, and 1st order reaction for the rest of the fixation period; Cu—2nd order reaction; and As—1st order reaction in red pine and aspen, and 2nd order in red maple. Rates of reaction decreased with increased CCA solution concentration for Cr and Cu, and increased for As, except in red maple. Reaction rates for all CCA elements were significantly higher in rapidly fixing red maple than in regularly fixing red pine and aspen, and were higher in unextracted than pre-extracted red maple. Modeling of CCA fixation kinetic for the whole fixation period enabled comparison of fixation reactions among wood species, preservative components, and treatment retentions.     

Reactions between Cr(VI) and wood and its model compounds

Wood, macromolecular and simple model compounds, were reacted with CrO₃ or K₂CrO₄ aqueous solutions. Extracted lignin, guaiacol, vanillin, vanillyl alcohol and homovanillyl alcohol were chosen as model compounds for lignin, whilst cellulose, gum Ghatti, xylan, extracted hemicellulose from pine, methyl-β-D-glucopyranoside and methyl-β-cellobioside were used as models for wood polysaccharides. The kinetics of the reduction reactions of Cr(VI) were monitored using UV-Vis spectroscopy and the results obtained for several temperatures are discussed. In general terms, wood, lignin and lignin model compounds reduced Cr(VI) faster and to a greater extent than polysaccharides or simple sugar molecules. Moreover, lignin model compounds were reduced even faster than lignin. Simple sugars showed a reduction pattern similar to that of cellulose. Extracted hemicellulose revealed to be a poorer reductant while gum Ghatti was the strongest among the polysaccharides. As expected, CrO₃ aq. behaved as a more powerfull oxidant than K₂CrO₄ aq. for these substances. Even at 100 °C, sugars or polysaccharides did not seem to be oxidised by K₂CrO₄ aq. 0.01 M. These results suggest that, because of the differences in reactivity, lignin reacts preferentially when wood is treated with Cr(VI)-containing formulations, like those which are applied in wood preservation treatments.     

Detection of glue deficiency in laminated wood with pulse thermography

 Adhesion problems sometimes occur during the production of laminated wood products. To minimize such quality problems, there is a need for a nondestructive test that can provide continuous control of the process and the product. This study presents results from measurements performed to evaluate the potential of pulse thermography as a method to detect glue deficiency in laminated wood. Defect depth, defect size, and degree of glue deficiency have been varied. The surface layer was made of merbau (Intsia bijuga) and the substrate of Scots pine (Pinus silvestris). The results showed that pulse thermography is a promising tool for detecting glue deficiency underneath the thin laminated wood surface layers, mainly because of the short inspection time. Lack of glue with a minimum thermal defect size of 3 was detectable (thermal defect size is defined as the quotient of defect size and defect depth). The penetration depth was 1.0 mm and the highest contrast, 0.62°C, was achieved for one of the largest defects (24 mm) below the thinnest (0.5 mm) surface layer after 1 second. Starved glue joints showed about half the contrast compared to areas with total lack of glue. Received: April 24, 2002 / Accepted: July 26, 2002 Acknowledgments We gratefully acknowledge the support of this work from the Knowledge Foundation and The Swedish Wood Association.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin V: effects of steam pretreatment

This study evaluated the potential of steam pre-treatment for making highly compressed phenol-formaldehyde (PF) resin-impregnated wood at a low pressing pressure. Sawn veneers of Japanese cedar (Cryptomeria japonica) were first subjected to saturated steam at different steaming temperatures (140°-200°C), followed by impregnation with a 20% low molecular weight PF resin aqueous solution resulting in a weight gain of around 50%-55%. Four oven-dried treated veneers were laminated and compressed up to a pressing pressure of 1 MPa at a pressing temperature of 150°C and pressing speed of 5 mm/min, and the pressure was held for 30 min. Steam treatment, causing partial hydrolysis of hemicellulose, accelerated the compressibility of Japanese cedar in the PF resin-swollen condition. As a consequence, a discernible increment in density was achieved at a pressing pressure of 1 MPa due to steam pretreatment between 140° and 200°C for 10 min. It was also found that even a short steaming time such as 2 min at 160°C is sufficient for obtaining appreciable compression of PF resin-impregnated wood. The density, Young’s modulus, and bending strength of steam-treated (200°C for 10 min) PF resin-impregnated wood composite reached 1.09 g/cm³, 20 GPa, and 207MPa, respectively. In contrast, the values of untreated PF resin-impregnated wood composite were 0.87 g/cm³, 13 GPa, and 170MPa, respectively.