Pyrolysis reactions of Japanese cedar and Japanese beech woods in a closed ampoule reactor

The chemical structures of hemicellulose and lignin are different for two distinct types of wood, i.e., softwood and hardwood. Such differences are expected to affect pyrolysis behavior. In this article, the differences are discussed for Japanese cedar wood (a softwood) and Japanese beech wood (a hardwood) pyrolyzed in a closed ampoule reactor (N₂/600°C/40–600 s). Oven-dried samples were used to eliminate the influence of initial water. Demineralized samples (prepared by acid washing) were also used to determine the influence of the minerals contained in the wood samples. As a result, some features were disclosed for secondary char (coke) formation, char reactivity, tar formation, and subsequent decomposition.     

水性树脂底漆对木材表面润湿性的影响

水性树脂底漆对木材表面润湿性能的影响是决定木器涂装质量的关键因素.为了给木器水性漆涂装提供基本依据,选择松木、杉木、橡木、奥古曼和非洲紫檀5种木材,研究水性丙烯酸树脂底漆、水性丙烯酸改性聚氨酯底漆、双组分水性丙烯酸树脂对其表面润湿性能的影响.采用正交试验设计方案,以漆种、底漆质量分数、树种和干磨砂纸粒度为影响润湿性的因...     

Improved water repellency of black spruce wood surfaces after treatment in carbon tetrafluoride plasmas

Plasma treatments for black spruce wood (Picea mariana (Mill.) B.S.P.), a widespread forest species from Canada, were carried out in order to waterproof the exposed surfaces. Experiments were performed using inductively coupled argon plasma with carbon tetrafluoride as the gaseous precursor for plasma-enhanced chemical vapor deposition of functional fluoropolymer coatings on wood. Analysis of the wettability through water contact angle measurements showed water-repellent characteristics, with static contact angles up to 130° depending on plasma exposure time, CF₄ concentration in the Ar/CF₄ plasma, and plasma source-to-substrate distance. X-ray photoelectron spectroscopy investigations of plasma-treated wood surfaces confirmed the growth of a thin, fluorocarbon layer with fluorine atomic concentrations close to 50 % on highly hydrophobic wood surfaces. Estimation of the thickness of the coatings by stylus profilometry revealed that a minimum layer thickness of about 80 nm is required to obtain water repellant wood surfaces with minimum water uptake. This complete set of data indicates that fluorocarbon-containing plasmas represent a very promising approach for improving the durability of wood products in wet and humid conditions.     

Multifunctional sol-gel coatings for protection of wood

Abstract

Organic–inorganic hybrid sol-gel coatings derived from sols synthesized using two organically modified precursors were generated on wood specimens using dip and spray coating techniques. One of the sols was synthesized using methacryloxypropyltrimethoxysilane (MPTMS) and nanoscaled boehmite particles and the other was synthesized using dimethyldiethoxysilane (DMDEOS) and tetraethoxysilane (TEOS). The coatings were generated on the wood specimens by dipping into the sols for specific time periods and by using spray coating method. The coatings were cured at different temperatures for varying soaking times. The dipping times, curing temperature, and soaking times were varied between 24–96 h, 130–200°C and 1–5 h, respectively. The coated samples were characterized for their water contact angles, microstructure, and resistance to water uptake. The coatings derived from MPTMS+boehmite sol were seen to exhibit better performance than DMDEOS+TEOS sol by forming a good barrier on the wood surface, thereby providing superior resistance to water and weather. Dipping of wood into the sol was seen to provide better protection when compared to spray coating. Dipping into the MPTMS+boehmite sol for 24 h and curing at 130°C for 2 h were found to be the optimal processing parameters yielding the best properties.     

甲基三甲氧基硅烷浸渍改性刨花板及其性能分析

刨花板是家具制造业的首选板材,在潮湿的环境中使用易出现翘曲变形、膨胀及分层等现象。为改善刨花板防潮性能,提高其尺寸稳定性,将甲基三甲氧基硅烷(MTMS)与0.1mol/L的盐酸以4∶1的体积比混合,将混合溶液置于冰浴中超声水解360 min,然后利用MTMS水解溶液对刨花板进行5 min的浸渍处理。分析了改性前后刨花板的润湿性、抗紫外老化性、粗糙度、表面化学结构及物理力学性能。研究结果表明:经MTMS水解溶液浸渍改性的刨花板具有稳定的拒水、拒油及抗老化性能,尺寸稳定性得到改善,板坯的表面密度增加,力学性能提高。     

超疏水纤维素复合气凝胶的制备及其油水分离

纤维素气凝胶因具有强亲水性和低油水选择性,且目前纤维素气凝胶表面的疏水化处理过程较冗长,限制了其在油水分离领域的应用。为了解决上述问题,笔者以硫酸水解微晶纤维素制备得到的纳米纤维素(CNC)为原料,利用甲基三甲氧基硅烷(MTMS)在水相中对其进行硅烷化改性,通过冷冻干燥得到了硅烷化纤维素复合气凝胶。结果表明:所制备的纤维素复合气凝胶具有轻质、多孔特性,随着MTMS添加量的增加,密度逐渐升高(≤0.012 0 g/cm^3),孔隙率略有下降; MTMS的加入对纤维素复合气凝胶的微观形貌影响不大,其骨架结构以二维片层形貌为主,聚甲基硅氧烷均匀地包覆在纤维素片层表面; MTMS的加入使纤维素复合气凝胶的热稳定性明显提高,且未改变纤维素气凝胶的晶型结构,但导致其结晶度逐渐下降。纤维素复合气凝胶的表面接触角随着MTMS添加量的增加而升高,最高达到153.7°,表现出优异的超亲油/超疏水性能。作为吸油材料,超疏水纤维素复合气凝胶不仅可以吸附多种油类和有机溶剂(吸附容量达到52～121 g/g),而且表现出很好的循环使用性能。     

Selective assessment of duplex heat-treated wood by near-infrared spectroscopy with principal component and kinetic analyses

We selectively assessed the thermal and hygrothermal treatment times of duplex heat-treated samples from the softwood hinoki cypress (Chamaecyparis obtusa) and the hardwood Japanese zelkova (Zelkova serrata) using near-infrared (NIR) spectroscopy with principal component analysis (PCA) and spectral-kinetic analysis. Wood samples from each species were thermally or hygrothermally treated at 120, 130, 150, and 180 °C, and the second-derivative spectra of these samples in the 6300–5450 cm^?1 range, where moisture content has the smallest effect, were then subjected to PCA. The master curve that was calculated by kinetic analysis successfully explained changes in the first principal component (PC1) scores with thermal treatment time for all temperatures. The angles between the PC1 loadings that explained the spectral variation due to thermal and hygrothermal treatment were 79° for hinoki and 80° for zelkova. Thus, calculation of the inner product between the second-derivative spectra of duplex heat-treated wood and a loading vector that explained the spectral variation due to thermal or hygrothermal treatment allowed us to selectively assess the thermal and hygrothermal treatment times.     

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.     

Reinforcement of fiberboard containing lingo-cellulose nanofiber made from wood fibers

Wood-based materials are fabricated with adhesives composed of various materials derived from fossil fuels. It is difficult to identify replacements for these chemical adhesives. This study explored nanofiber technologies as an alternative to these adhesives. In this study, we focused on reinforcement effects of lingo-cellulose nanofiber (LCNF) on fiberboards made from softwood and hardwood fiber. We discuss the density effects of reinforcement with LCNF because the density of medium-density fiberboard (MDF), which is widely used for construction, is standardized at about 0.60–0.80 g/cm³. Fiberboards were manufactured with three densities (0.60, 0.75, and 1.00 g/cm³). For softwood fiberboards, the bending properties for LCNF-mixed boards were higher than those for the control fiberboards at all densities. In this paper, control fiberboard means fiberboard with fiber only. For hardwood fiberboards, the bending properties for LCNF-mixed fiberboard for 1.00 g/cm³-density board were higher than those for the control fiberboard. For internal bond strength (IB), the IB for LCNF-mixed fiberboard was higher than that for the control fiberboard. The thickness swelling (TS) and weight change (WC) with water absorption for fiberboards containing LCNF were lower than those for control fiberboards. As a conclusion, physical and mechanical properties of the resulting fiberboards were significantly improved with the addition of LCNF, especially for softwood fiberboards, due to close binding between LCNF and wood fibers.     

Wood decaying properties of the termite mushroom <Emphasis Type="Italic">Termitomyces eurrhizus</Emphasis>

Four strains of the termite mushroom Termitomyces eurrhizus collected in Japan were surveyed for their wood decaying properties in three softwood and two hardwood species, in comparison with the white-rot fungus Trametes versicolor and the brown-rot fungus Fomitopsis palustris. All strains of T. eurrhizus degraded only the surfaces of the wood samples, and differences in mass-loss rates between heartwood and sapwood were generally not significant. Higher mass-loss rates were generally obtained in softwood than in hardwood. The results of chemical analyses of decayed wood samples indicated that T. eurrhizus does not have high lignin-degradation ability, even though it is categorized as a white-rot fungus. These results clearly suggest the unique physiological characteristics of T. eurrhizus.     

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     

The fractal estimation of wood color variation by the triangular prism surface area method

Color variations of the surfaces of fifteen wood species were characterized by fractal dimension of the triangular prism surface area method. Softwood and hardwood indicated apparently different in the mean fractal dimensions of red and green colors. Red color behaved steadier in softwood than in hardwood and green color varied comparatively stronger in hardwood than in softwood. No evident differences between softwood and hardwood were found in the variation of blue color of all the specimens. Following the low-to-high value order of the mean fractal dimensions, three types of combination of red (R), green (G) and blue (B) colors were found: RGB, RBG and BGR. There also existed six types of fractal dimension distribution; namely, plane, included plane, concave, convex, zigzag, and hilly distributions. Fractal dimensions across the grain changed greatly whereas those along the grain became relatively steady. The characteristic difference of color variation was defined for each species, which was inferred to characterize its own unique appearance of surface color. For color matching of wood parts, fractal dimension quantitatively furnishes essential information of color variation in local and overall features. Such evaluation can be efficiently carried out with few measurements along the grain and by detecting a single color (red, green or blue) only. Received 5 May 2000     

Micropores and mesopores in the cell wall of dry wood

To investigate micropores and mesopores in the cell walls of dry wood, CO₂ gas and N₂ gas adsorption onto dry wood were measured at ice-water temperature (273 K) and liquid nitrogen temperature (77 K). CO₂ gas adsorption isotherms obtained were used for determining micropore volumes smaller than 0.6 nm by the HK method (Horvath-Kawazoe method), and N₂ gas adsorption isotherms obtained were used for determining the mesopore volume between 2 nm and 50 nm by the Barrett-Joyner-Halenda (BJH) method. Micropores and mesopores existed in cell walls of dry wood, and the cumulative pore volume was much larger for micropores than for mesopores. Micropores in the cell wall of dry wood decreased with elevating heat treatment temperature, and the decreased micropore was reproducible by wetting and drying. Mesopores did not decrease so much with elevating heat treatment temperature. Micropore volumes for the softwood Hinoki and the hardwood Buna were compared. A larger amount of micropores existed in hardwood Buna than in softwood Hinoki, and this relationship was considered to correspond to the difference in thermal softening properties for lignin in water-swollen Hinoki and Buna. This result probably indicates that micropores in the cell walls of dry wood relate to the structure of lignin.     

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.     

Thermally initiated solvent-free radical modification of beech (Fagus sylvatica) wood

A procedure for rapidly modifying beech wood using a thermally initiated solvent-free grafting system was examined. In the modification, butyl acrylate and butyl methacrylate were used as vinyl monomers. Free radicals were generated from 2,2′-azobis(2-methylpropionitrile) or benzoyl peroxide at 103 and 180 °C by contact heating of the modified material. Chemical changes in the material were investigated by FTIR and X-ray photoelectron spectroscopies. The modification resulted in decreased surface wetting of the material manifested by increased water contact angles. The hardness of the resultant material decreased, while its color changed by the effect of temperature. It was shown that the approach allowed for efficient thermal-initiated modification of wood with rapid contact heating.     

微波等离子体处理对杉木表面性能的影响

为了解微波等离子体处理对杉木表面性能的影响,使用接触角测定评估表面润湿性,使用扫描电子显微镜观测表面处理前后的差异。结果表明,杉木表面轻微波等离子体处理后,接触角下降为零,即使处理条件十分微弱、处理效果仍然十分明显,这表明微波等离子体处理可显著提高木材表面的润湿性,微波等离子体处理使杉木表面形成粗化面,即表面明显有等离子体蚀刻过的痕迹并留下凹凸不平的坑洼,粗化面的形成可能是导致杉木表面接触角下降,     

Assessing VOC emission by different wood cores using the PTR-ToF-MS technology

To date, the chemical composition and the amount and diversity of volatile organic compounds (VOCs) released by different woody plants samples have been measured and characterized through one of the most common techniques, the gas chromatography–mass spectrometry. However, this technique is very time-consuming and requires sample preparation. By contrast, the Proton-Transfer-Reaction Time-of-Flight Mass spectrometry (PTR-ToF-MS) represents an innovative tool able to provide the whole mass spectra of VOCs with short response time, high mass resolution and without sample preparation. This technique is fast, non-invasive, highly sensitive with a rapid detection system and a very low mass fragmentation of the volatile molecules. The goal of this study was to characterize the VOCs profile of different wood sample cores using a PTR-ToF-MS tool and thereafter to assess whether VOC emissions were specific for some groups of trees. VOCs released from core wood samples belonging to 14 different species were analyzed and subsequently, using an advanced multivariate class-modeling approach, the groups (softwood and hardwood) and the different tree species were discriminated. PTR-ToF-MS was able to detect VOCs from wood and to discriminate between hardwood and softwood and among different species. The great potential and the rapidity of this analysis method allow the PTR-ToF-MS to become a commercial standard tool for monitoring VOCs emitted by wood.     

木材（特征图象）的微机识别

通过对“微机辅助木材识别系统WIP-89”项目的发展和增补,在木材识别方式上有新的突破,即通过木才解剖图象,微机自动识别木材,现已解决针对树材中的早材至晚材,急变和渐变;阔叶树材中的环孔材、半环孔材和散孔材。     

Effect of ACQ-D treatment on the surface free energy of Chinese fir (<Emphasis Type="Italic">Cunninghamia lanceolata</Emphasis>)

In this study, the contact angles of three different reference liquids （including distilled water, diiodomethane, and formamide） and PF resin on the surfaces of Chinese fir （Cunningharnia lanceolata） samples untreated or treated with different concentrations of ACQ-D （ammoniacal copper quat Type D） solutions were measured. Then, the surface free energy was calculated by two approaches： acid-base approach and geometric mean approach. ACQ-D treatment caused higher contact angles and lower surface free energies at a retention level corresponding to the commodity treated wood products. When wood was treated with much higher concentrations of ACQ-D, the total surface free energy of wood would be higher than the untreated control. Acid-base/polar components related with the hydrogen bonding state in wood were considered to be responsible for the observed changes according to the applied approaches. The hydrophobic properties and also higher contact angles of PF resin drop on wood surfaces after ACQ-D treatment at a reasonable retention level confirms the changes on surface free energy.     

Differential calometric analysis of wood and wood components

Summary The prolysis of cellulose, hemicelluloses, lignin preparations, and wood was studied by differential calorimetric analysis (DCA) for the range of 25° to 800° C. The test samples included powdered and filter paper celluloses; hardwood xylan; softwood galactoglucomannans, compression wood galactan, and arabinogalactan; a synthetic (DHP), sulfuric acid, Björkman, Brownell, and cellulase lignins; and unextracted and extracted hardwoods and softwoods. Heats of reaction were determined from the DCA thermal transition areas. Distinct differences were found between the thermograms of each hemicellulose and lignin sample. Although wood species could not be separated thermally, hardwood and softwood thermograms differed because of the hemicellulose degradation pattern.Trade names and company names are included for the benefit of the reader and do not imply any endorsement or preferential treatment of the product by the U.S. Department of Agriculture.Formerly Research Technologist, Forest Products Laboratory, Forest Service, U.S. Department of Agriculture. The Laboratory is maintained at Madison, Wis. 53705, in cooperation with the University of Wisconsin. Present address: The Pennsylvania State University, University Park, Pennsylvania 16802.