Modelling moisture-related mechanical properties of wood Part II: Computation of properties of a model of wood and comparison with experimental data

Starting with simple concepts of the molecular structure and models of the stiffness and swelling behaviour of lignin, hemi-cellulose and cellulose and building up through the various levels of organisation in the wood cell wall a model has been constructed that simultaneously predicts the variation with moisture content change of both the longitudinal Young's modulus and longitudinal shrinkage of wood. The model closely predicts both longitudinal shrinkage and Young's modulus as they vary with the moisture content of the wood. The model also takes into account structural variations in the form of changes in cell wall layer thicknesses and mean cellulose microfibril orientation.     

Origin of the characteristic hygro-mechanical properties of the gelatinous layer in tension wood from Kunugi oak (Quercus acutissima)

The mechanism responsible for unusual hygro-mechanical properties of tension wood containing the gelatinous layer (G-layer) was investigated. Tension and normal wood specimens were sampled from the leaning stems of a 75- and a 40-year-old Kunugi oak (Quercus acutissima) tree, and the moisture dependencies of the longitudinal Young’s modulus and longitudinal dimensions were measured. The results, which were analyzed in relation to the anatomical properties of the specimens, revealed that the ratio of increase in the longitudinal Young’s modulus with drying was higher in the G-layer than in the lignified layer (L-layer); the longitudinal drying shrinkage displayed a similar pattern. It was found that the lattice distance of the [200] plane in the cellulose crystallite increased with drying, moreover, the half-width of the [200] diffraction peak increased with drying, which was remarkable in the tension wood. Those results suggest that in the green state, the polysaccharide matrix in the G-layer behaves like a water-swollen gel; however, it is transformed into a condensed and hard-packed structure by strong surface tension during moisture desorption, which is a form of xero-gelation. However, in the L-layer, condensation and subsequent xero-gelation of the polysaccharide matrix was prevented by the hydrophobic lignin that mechanically reinforces the matrix.     

Chemical structural elucidation of total lignins in woods I: fractionation of the lignin in residual wood meal after extraction of milled wood lignin

Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

Impact of moisture content on dynamic mechanical properties and transition temperatures of wood

The dynamic shear modulus and the loss modulus of Betula alba, Ulmus parvifolia, Quercus robur, Acer platanoides, Tilia cordata, Fraxinus excelsior and Pinus sylvestris wood were measured using an inverted torsion pendulum within a wide temperature range. The glass transition temperature of the lignin–carbohydrate complex and the decomposition temperature of the wood cellulose were estimated. The temperature band from 170°C to 240°С shows the transition of the lignin–cellulose complex from the glassy to the rubbery state. Mechanical properties of different types of wood are affected by moisture and anatomical differences, but glass transition and decomposition temperatures are the same. More than 5% of moisture in the wood stored at normal conditions were found. After drying, the increase of dynamic shear modulus of wood over the entire region of the glassy state was observed. The intensity of maximum peak of dynamic loss modulus is also increased due to activation of the segmental motion of macromolecules of the ligno-carbon complex. The decomposition temperature of the cellulose crystallites was unchanged for specimens containing moisture and for dried specimens.     

Multivariate modeling of acoustomechanical response of 14-year-old suppressed loblolly pine (<Emphasis Type="Italic">Pinus taeda</Emphasis>) to variation in wood chemistry,microfibril angle and density

The polymeric angle and concentration within the S₂ layer of the softwood fiber cell wall are very critical for molecular and microscopic properties that influence strength, stiffness and acoustic velocity of wood at the macroscopic level. The main objective of this study was to elucidate the effect of cellulose, hemicellulose, lignin, microfibril angle and density on acoustic velocity and material mechanical properties of 14-year-old suppressed loblolly pine. Cellulose, hemicellulose and density are consistently the most important drivers of strength, stiffness and velocity. Cellulose and lignin are the highest and lowest contributor to velocity, respectively, with lignin acting as a sound wave dispersant, while cellulose is the most important conductor of sound wave at the molecular level, while hemicellulose acts as a special coupling agent between these components. The polymeric constituents are thus important drivers of sound wave propagation at the molecular level, while density played a subsequent role at the macroscale.     

Nondestructive estimation of wood chemical composition of sections of radial wood strips by diffuse reflectance near infrared spectroscopy

The use of calibrated near infrared (NIR) spectroscopy for predicting the chemical composition of Pinus taeda L. (loblolly pine) wood samples is investigated. Seventeen P. taeda radial strips, representing seven different sites were selected and NIR spectra were obtained from the radial longitudinal face of each strip. The spectra were obtained in 12.5 mm sections from pre-determined positions that represented juvenile wood (close to pith), transition wood (zone between juvenile and mature wood), and mature wood (close to bark). For these sections, cellulose, hemicellulose, lignin (acid soluble and insoluble), arabinan, galactan, glucan, mannan, and xylan contents were determined by standard analytical chemistry methods. Calibrations were developed for each chemical constituent using the NIR spectra, wood chemistry data and partial least squares (PLS) regression. Relationships were variable with the best results being obtained for cellulose, glucan, xylan, mannan, and lignin. Prediction errors were high and may be a consequence of the diverse origins of the samples in the test set. Further research with a larger number of samples is required to determine if prediction errors can be reduced.     

Mechano-sorptive creep mechanism of wood in compression and bending

Summary A model is introduced which links the mechano-sorptive behaviour of wood subjected to moderate and high compression or bending stresses parallel to grain to the formation of slip planes in the cell wall. Slip plane formation is dependent on the breaking of hydrogen bonds, which process is directly related to the amount of moisture change. The dramatic change of microfibril orientation in slip plane zones cause an increase of the longitudinal shrinkage/swelling and a decrease of the modulus of elasticity. These features of slip plane formation account for both the magnitude and the oscillation of the excessive mechano-sorptive creep associated with compression and bending parallel to grain. A summary is given of the characteristics of the mechano-sorptive effects, and the model is discussed in the light of these effects.The paper is one of the results of a project on the influence of changing moisture content on the mechanical behavior of wood, currently underway in a co-operation between College of Environmental Science and Forestry, State University of New York, and the Technical University of Denmark. Support for this project is provided by the Danish Technical Research Council and by the USDA C--operative Research Program (proj. 85-FSTY-9-0112). The support is gratefully acknowledged     

古建木构件化学组分近红外光谱分析

在材种鉴定的基础上,通过近红外光谱(NIRS)定性分析了建成约600 a的木造古建筑木构件的化学组分,结合木构件化学组分定量分析,与现代木材相比较,探讨了近红外光谱技术评价木构件老化的可行性。结果表明:近红外二阶导数特征性谱带反映了木材纤维素以及半纤维素和木质素的基团信息,而其差谱反映出木构件与对照样化学组分变化。这些光谱特征与传统的化学组分定量分析的结果非常一致:纤维素和半纤维素相对含量减少而木质素相对含量增加,与各种组分谱带差谱的增减相对应。此外,在5 882,5 587和5 464 cm-1等谱带处反映的纤维素结晶和半结晶区的光谱信息,差谱观察到木构件与现代材落叶松之间化学组分的不变或减少,其结果与X射线衍射(XRD)方法获得的木材结晶度分析结果相一致。通过NIRS定性分析木构件化学组分及结晶度变化,接近于现场检测方法,使用便携式NIRS,在古建筑木构件端头裸露部位获取光谱信息,能够实现现场对木材化学组分的无损定性评价。本实验结果也表明,除了常规的红外光谱(FT-IR)、XRD分析技术,NIRS技术对于木构件老化状况的评价是一种有潜力的无损检测方法。     

Properties of cell wall constituents in relation to longitudinal elasticity of wood

 To predict the origin of longitudinal elasticity of the solid wood in relation to the composite structure of the wood cell wall, an analytical procedure was developed on the basis of the idea of “the reinforced-matrix hypothesis” originally introduced by Barber and Meylan (1964). A multi-layered circular cylinder, having the CML, the S1, and the S2 layers, was used as a model of the ligno-cellulosic (wood) fiber, and the elastic properties of an isolated wood fiber were formulated mathematically. In the formulation, not only the structural factors, such as the microfibril angle and the thickness of each layer, but also the environmental condition, e.g. the moisture content, were taken into consideration. The effects of the moisture content and the microfibril angle upon the longitudinal Young's modulus and the Poisson's ratio of the wood fiber were simulated by using the newly derived formulae. It is anticipated to give a start to estimate the fine structure and the internal properties of the cell wall constituents in relation to the macroscopic behaviors of the wood through simulating the mechanical behaviors of the wood fiber. Received 17 August 1999     

Modelling longitudinal elastic an shrinkage properties of wood

Summary A model was developed for estimating elastic and shrinkage properties of a softwood cell wall from the properties of its polymeric constituents: cellulose, hemicellulose and lignin. The theory of composite materials was used. Based on a literature survey, models of latewood, earlywood and compressionwood of a softwood cell wall structure were made. The model takes into account the helical winding of the microfibrils in the cell wall and it estimates the behaviour of a balanced laminated double-cell wall in which rotation is restrained by adjacent cells. The calculated elastic and shrinkage properties were compared with earlier test results and good agreement was found.     

Young's modulus of hemicellulose as related to moisture content

Summary The Young's modulus of hemicellulose extracted from Pinus radiata wood has been measured by an indentation method. Values obtained for the modulus varied by almost three orders of magnitude, from 8.0×10⁹ Pa in nearly dry hemicellulose to 1.0×10⁷ Pa in nearly saturated hemicellulose. The very low value of the modulus at high moisture contents has some interesting implications for models of the mechanical behaviour of the wood cell wall.     

Micropore structure of wood: Change in micropore structure accompanied by delignification

In our preceding study, we clarified that liquids having similar molecular sizes to ethanol were mainly adsorbed onto lignin among the major constituents of wood. This suggests that most micropores or adsorption sites loosely hydrogen-bonded to each other, which are accessible to these liquids, exist in lignin. In the present study, to examine micropores in wood and lignin, micropore distribution was measured by CO₂ gas adsorption at ice-water temperature (273 K). Dry samples prepared by gradual delignification from wood meal were used as adsorbents. The pore-size distributions were determined by analyzing adsorption isotherms using the Horvath-Kawazoe method. It was found that the number of micropores decreased with the decrease in residual lignin, and micropores were hardly found in cellulose and hemicellulose. It is considered that most micropores smaller than 0.6 nm in wood exist in lignin.     

Micromechanics of wood subjected to axial tension

Summary The behaviour of a small group of wood fibers of Sitka spruce during tensile loading is investigated. The load-extension curves for both early and late wood fibers consist of three distinct segments. The first segment is almost a straight line, at some stage of loading a yield point is observed. Beyond this point the specimen becomes less stiff and undergoes a large, mainly irreversible deformation. As the load is increased further, the curve exhibits the third segment showed by a significant change in slope. These curves look different from those obtained on thick specimens. In this respect, the behaviour of a thin wood specimen subjected to cyclic type tensile loading along its longitudinal direction is also illustrated. Based on wood microstructure, a model is presented to interpret the evolution of the Young's modulus of a wood fiber during tensile loading. The model considers wood as an assembly of cylindrical fibers pasted together in a longitudinal direction. We have assumed the cell wall to comprise only an S₂ layer made of a composite material consisting of a lignin and hemicellulose matrix reinforced by helical microfibrils along the fiber. Furthermore, it is assumed that the microfibril angle a in the S₂ layer is not uniform along the fiber axis and matrix degradation occurs in the zones where the microfibril angles are bigger. The validity of this assumption is verified by using holographic interferometry to visualize the displacement field of the specimen's surface under tension.The work reported in this paper is supported by a grant from the Swiss National Science Foundation, and its support is gratefully acknowledged     

Effect of acetylation on the chemical composition of hornbeam (Carpinus betulus L.) in relation with the physical and mechanical properties

Common hornbeam (Carpinus betulus L.) is a highly underused wood species despite its great hardness, strength, wear-resistance and toughness. It is mainly used as firewood in Hungary because of its wood defects, irregular shape and low-dimensional stability. These wood defects and small breast height diameter result in a low yield. It is non-durable outdoors as it tends to turn grey, crack and be attacked by wood-decaying organisms. Indoors it lasts for hundreds of years. One technology that could improve the stability and durability properties is acetylation. Hornbeam was acetylated with the Accoya® method under industrial conditions. The aim of this research was the assessment of acetylation affecting the chemical properties of hornbeam wood and how these are related to the change in physical and mechanical properties. Main wood constituents (cellulose, hemicellulose, Klason lignin, extractives and ash content) were determined and compared. Chemical parameters related to the degradation of structural polymers were also evaluated (total phenolic and soluble carbohydrate contents, pH and buffering capacity, furfural, levulinic acid, formic acid, acetic acid). Structural changes in acetylated wood and in the Klason lignin fraction were also assessed using FTIR spectroscopy.     

Behavior of the cellulose microfibril in shrinking woods

We measured the longitudinal and tangential shrinking processes in wood specimens from Chamaecyparis obtuse Endl. with different microfibril angles (MFAs). The shape of the shrinking curve was compared with the MFA. Only the longitudinal shrinking process of specimens with a small MFA clearly showed nonlinearity, and the degree of nonlinearity increased as the MFA decreased. In contrast, the tangential shrinking process and the longitudinal shrinking process of compression wood with a large MFA were linear. The nonlinearity is probably caused by the longitudinal shrinkage of the noncrystalline region of the cellulose microfibril (CMF) in regions of low moisture content during water desorption. When the moisture content is high, the matrix substance in the cell wall begins to dry; however, the shrinkage in the chain direction is restrained by the rigid CMF. As the wood dries further, the noncrystalline region of the CMF embedded in the matrix substance begins to shrink. Because the longitudinal mechanical behavior of wood with a small MFA is greatly affected by a rigid CMF, longitudinal shrinkage increases suddenly at about 10% moisture content; as a result, the shrinking process shows nonlinearity.     

A model of the anisotropic swelling and shrinking process of wood. Part 1. Generalization of Barber's wood fiber model

Summary The anisotropic mechanism of wood swelling and shrinkage was investigated theoretically. The reinforced-matrix hypothesis offered by Barber and Meylan (1964) was reformulated by using a multi-layered wood fiber model, and the formula describing the dynamical behavior of swelling and shrinking wood fiber was derived. For modelling, the moisture content changes were taken into consideration as an explicit parameter. It is expected to predict the anisotropic swelling and shrinking process of wood dynamically and quantitatively, as well as to initiate elucidating the interaction between the moisture and cell wall components on the basis of the present model. Some concrete calculations will be demonstrated in the following report, and the results will be compared with the experimental ones. Received 2 September 1997     

Vibrational properties of heat-treated green wood

To investigate the influence of water on heat treatment, green wood was heat-treated. Sitka spruce (Picea sitchensis Carr.) with about 60% moisture content (MC) was used. Young's modulus and loss tangent were measured by the free-free flexural vibration test. The specimens were heated in nitrogen at 160°C for 0.5h. The results were as follows. (1) Recognizing that the effects of heat treatment are mild and that the same specimens cannot be used for both heat treatment and as controls, it was necessary to investigate the effects of the heat treatment based on the variations of properties in the whole of the test lumber. (2) Young's modulus increased and the loss tangent decreased due to heat treatment. When the vibrational properties were measured at various MCs, the MCs at the maximum value of Young's modulus and the minimum value of the loss tangent were lower in heat-treated specimens than in controls. The effects of heat treatment in green wood were similar to those in air-dried wood. (3) The loss tangents of heat-treated specimens were smaller than those of controls at about 0% MC but were larger than those of controls at about 10% MC. We thought that this resulted from the decreased MC at the minimum loss tangent after the heat treatment mentioned above. (4) The properties measured at several MCs were more useful than those at only one moisture content for investigating the effects of heat treatment.This study was presented in part at the 46th annual meeting of the Japan Wood Research Society, Kumamoto, April 3–5, 1996; and at the 47th annual meeting of the Japan Wood Research Society, Kochi, April 3–5, 1997     

The generation of longitudinal maturation stress in wood is not dependent on diurnal changes in diameter of trunk

A hypothetical mechanism for the generation of maturation stress in wood was tested experimentally. The hypothesis was that the maturation stress could partly originate in a physical mechanism related to daily changes in water pressure and associated diurnal strains. The matrix of lignin and hemicellulose, deposited in the cell wall during the night, would be put in compression by the effect of water tension during the next day. The cellulose framework, crystallizing during the day, would be put in tension by the decrease in tension at night and subsequent cell-wall swelling. This was tested on young saplings of sugi and beech. Half of the saplings were submitted to continuous lighting, which canceled diurnal strains. Saplings were tilted 40 degrees, and their uprighting movement was measured. The uprighting movement is directly due to the production of reaction wood and the concomitant development of large longitudinal maturation stress. It occurred in the continuously lighted plants at least as much as in control plants. We conclude that the generation of longitudinal maturation stress in tension or compression wood is not directly related to variations in water pressure and diurnal strains.     

Enzymatic hydrolysis of wood with alkaline treatment

Pulverized samples of wood, cedar and eucalyptus were treated with 5 N NaOH solutions at 25–150 °C. Hemicellulose and lignin content in the samples decreased with increasing treatment temperatures, while the recovery of glucose was maintained at nearly 90 %. X-ray diffraction analysis showed that the content of the original cellulose I structure in the samples decreased with increasing temperature, and most of the cellulose in the sample treated at 150 °C was converted to cellulose II by mercerization. Enzymatic hydrolysis of the alkaline-treated samples was carried out at 37 °C using solutions comprising a mixture of cellulase and β-glucosidase. The samples treated at higher temperatures showed better enzymatic degradability. Treatment with an alkaline solution of lower concentration (1 N NaOH) at 150 °C was also used. Despite significant quantities of hemicellulose and lignin being removed, mercerization was not induced. The enzymatic degradability was much lower than that of the sample treated with a 5 N NaOH solution at 150 °C. Thus, treatment with concentrated alkaline solution at high temperature led to not only the removal of hemicellulose and lignin, but also to modification of the cellulose structure, which resulted in high efficiency of enzymatic saccharification of the wood samples.     

杨木应拉木微区结构可视化及化学成分分析

木材微区结构与木材宏观性质密切相关,杨木应拉木与对应木宏观性质存在较大差别,探究杨木应拉木和对应木微区结构和化学成分,可为了解杨木应力木的宏观性质提供理论根据。借助光学显微镜、荧光显微镜、显微拉曼成像光谱仪、透射电镜对杨木应拉木微区结构进行可视化研究,并借助X射线衍射技术和美国可再生能源实验室方法,分析杨木应拉木的微晶尺寸、结晶度以及化学成分。结果表明:杨木应拉木中应拉区和对应区纤维细胞微区结构差异显著。光学显微镜下显示应拉区木纤维中胶质层清晰可见,荧光显微镜和拉曼显微镜下显示胶质层的木质素浓度比对应区低。透射电镜下显示应拉区木纤维细胞壁结构由初生壁、次生壁和胶质层组成,未见次生壁外层,各层的平均厚度分别为0.61,1.22和2.53μm。对应区木纤维为典型的初生壁和次生壁结构,次生壁各层平均厚度分别为0.33,2.28和0.14μm。杨木应拉区纤维素含量(58.91%)比对应区(41.53%)高,木质素含量和半纤维素含量均比对应区的低,应拉区木质素和半纤维素含量分别为21.99%和12.01%,对应区分别为28.10%和17.08%。杨木应拉区结晶度(48.06%)比对应区(41.01%)高,应拉区晶区宽度为2.66 nm,长度为8.84 nm;对应区晶区宽度为2.65 nm,长度为9.87 nm。