Nanostructural assembly of cellulose,hemicellulose, and lignin in the middle layer of secondary wall of ginkgo tracheid

Physical, chemical, and biological properties of wood depend largely on the properties of cellulose, noncellulosic polysaccharides, and lignin, and their assembly mode in the cell wall. Information on the assembly mode in the main part of the ginkgo tracheid wall (middle layer of secondary wall, S2) was drawn from the combined results obtained by physical and chemical analyses of the mechanically isolated S2 and by observation under scanning electron microscopy. A schematic model was tentatively proposed as a basic assembly mode of cell wall polymers in the softwood tracheid as follows: a bundle of cellulose microfibrils (CMFs) consisting of about 430 cellulose chains is surrounded by bead-like tubular hemicellulose-lignin modules (HLM), which keep the CMF bundles equidistant from each other. The length of one tubular module along the CMF bundle is about 16 ± 2 nm, and the thickness at its side is about 3–4 nm. In S2, hemicelluloses are distributed in a longitudinal direction along the CMF bundle and in tangential and radial directions perpendicular to the CMF bundle so that they are aligned in the lamellae of tangential and radial directions with regard to the cell wall. One HLM contains about 7000 C₆-C₃ units of lignin, and 4000 hexose and 2000 pentose units of hemicellulose.     

The influences of boiling and drying treatments on the behaviors of tension wood with gelatinous layers in <Emphasis Type="Italic">Zelkova serrata</Emphasis>

This study examined how boiling and drying treatments influenced various physical properties of the tension wood with gelatinous fibers (G-fibers) of a 29-yearold Zelkova branch. By boiling treatment, tension wood with numerous G-fibers contracted considerably in the longitudinal direction and the longitudinal Young’s modulus decreased in spite of the water-saturated condition. The drying treatment caused green tension wood and boiled tension wood with numerous G-fibers to shrink longitudinally and increased their longitudinal Young’s moduli. These specific behaviors in tension wood were highly correlated with the proportion of G-fibers in a specimen and were probably caused by the microscopic behavior of cellulose microfibril (CMF) in the gelatinous layers (G-layers). The longitudinal shrinkage of tension wood due to drying suggests the existence of a hygro-sensible, noncrystalline region in the CMF, which is abundant in the G-layer. Furthermore, the noncrystalline region in the CMF softens during boiling treatment, resulting in the reduction of the longitudinal Young’s modulus in tension wood. The longitudinal contraction of tension wood with G-fibers by boiling might be caused by the tensile growth stress remaining in green G-layers. However, no changes were detected in the 004 d-spacing of cellulose crystal in tension wood from the boiling and drying treatments, regardless of the proportion of G-fibers.     

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.     

Changes in wettability of heat-treated wood due to artificial weathering

Effect of artificial weathering on the wettability of three heat-treated North American wood species (jack pine, aspen, and birch) is studied from the point of view of the structural and chemical changes taking place on the wood surface. Weathering increases wettability of all three heat-treated woods by water. Changes in wettability during artificial weathering differ according to heat treatment procedure and wood species and are likely due to combination of structural and chemical changes of the surfaces. Scanning electron microscopic analysis indicates that cracks form due to degradation taking place during weathering. As a result, water has easier entry into the cell wall, which consequently increases wettability. IR spectra suggest that the OH/CH₂ ratio for heat-treated specimens is inversely proportional to the contact angle regardless of the type of wood species. The presence of cellulose-rich layer on wood surface and increasing amount of amorphous cellulose transformed from crystallized cellulose due to weathering result in increase in hydroxyl; consequently, it increases heat-treated wood wettability.     

A literature-based study on the loss tangent of wood in connection with mechanical pulping

In mechanical pulping, wood is dynamically loaded, which causes large heat losses due to wood viscoelasticity. The heat losses depend on the loss tangent (tan δ) of wood. The loss tangent has a temperature-dependent behaviour, especially in the lignin glass transition region. The glass transition softens wood, and is therefore necessary for gentle mechanical pulping, but at the same time, the loss tangent shows a maximum called the α-peak. The transient peak depends on temperature, loading frequency and moisture content. The temperature where the peak is found can be lowered with chemical treatments, but they also increase the magnitude of the peak. Thermal treatment in the presence of water also increases the magnitude. The loss tangent of wood depends, amongst other things, on the chemical structure of lignin, width of cellulose crystals, microfibril angle, and extractives in the cell wall.     

Morphological changes in sugi (Cryptomeria japonica) wood after treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride

We investigated morphological changes in wood tissues of sugi (Cryptomeria japonica) resulting from treatment with the ionic liquid 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]), which dissolves cellulose. Treatment with [C2mim][Cl] caused dissociation and distortion of tracheids in latewood, but not in earlywood. This difference was due to the difference in swelling behavior of the cell wall between earlywood and latewood. Many pit membranes in bordered pits were broken by treatment with [C2mim][Cl]. In addition, some chemical changes in wood components, such as cellulose and lignin, occurred before significant disruption or destruction of the cell wall. Our results show that the reaction of wood liquefaction by [C2mim][Cl] treatment is not homogeneous, both from chemical and morphological viewpoints.     

Mechanical interaction between cellulose microfibril and matrix substance in wood cell wall determined by X-ray diffraction

We investigated mechanical interactions between the cellulose microfibril and the matrix substance in wood cell walls. X-ray diffraction measurements showed that the peak positions of (200) and (004) from cellulose crystals in wood cell walls tended to shift lower and higher toward 2θ, respectively, during water desorption in wood. From our simulations, it is shown that the peak shift of (200) during water desorption is not due to changes in the scattering pattern of the amorphous substance or to lateral expansion of the cellulose crystals due to the Poisson effect in the cellulose microfibril, which is compressed in the molecular chain direction as the amorphous substance shrinks. This suggests that the cellulose microfibril expands transversely during water desorption in the wood cell wall, and that there is a mechanical interaction between the cellulose microfibril and the matrix substance.     

Mechanics and pyrolysis analyses of rotation welding with pretreated wood dowels

This study examined the mechanics and pyrolysis analyses of rotation welding with treated dowels. Test results indicated that welding specimens with dowels immersed in CuCl₂ solution exhibited higher pullout resistance than untreated specimens. Scanning electron microscopy was used to observe and analyze the welding interface. Wood dowels immersed in CuCl₂ solution provided more flowing molten polymer to obtain better connection than untreated wood dowels. Based on the chemical analyses of X-ray photoelectron spectroscopy, and thermogravimetric analyses, the hydrolysis of cellulose and hemicellulose was detected after immersion of the dowels in a CuCl₂ solution. Pyrolysis of cellulose, hemicellulose and lignin occurred during the welding process. The hydrolysis of cellulose and hemicellulose may promote the pyrolysis and efficient connection of wood components during the welding process.     

A histological investigation of Oriental beech wood decayed by Pleurotus ostreatus and Trametes versicolor

Chemical, light and electron microscopic studies were carried out on wood of Oriental beech (Fagus orientalis Lipsky) decayed by the white‐rot fungi Pleurotus ostreatus and Trametes versicolor for 30, 60 and 120 days according to the modified European standard EN 113. Mass loss as well as lignin, cellulose and carbohydrate content were determined before and after fungal attack. There were no significant differences of wood mass loss and chemical composition between both fungi at the end of incubation. After each incubation period, small specimens were stained for microscopic studies. The micromorphology of fungal cell wall degradation was rather similar for both fungi. Both decreased the cell wall thickness to the same extent. The accumulation of hyphae as well as the rupture of cell walls was also similar. The occurrence of hyphae, cavities in the pits and vessel walls followed nearly the same patterns. The parenchyma cells were completely destroyed. Altogether, both fungi produced a simultaneous white rot in Oriental beech wood.     

Microfibril angle and density of hinoki (Chamaecyparis obtusa) trees in 15 half-sib families in a progeny test stand in Kyushu, Japan

It was previously believed in Japan that the wood qualities of hinoki (Chamaecyparis obtusa) were superior to sugi (Cryptomeria japonica). However, few studies of wood properties such as MFA (microfibril angle of S₂ layer in secondary wall of tracheid) have been completed for hinoki. Some reports have found that hinoki plus tree families have similar mechanical properties to sugi. Here we report the characteristics of MFA and density of hinoki half-sib families in a progeny test stand. There were significant differences in MFA and density between families. The wood properties of two families, Nakatsu 3 and Kanzaki 5, are stable in radial pattern and suitable for structural use. Early selection of hinoki families by MFA and density may be difficult. Effects of MFA and density on E _d (dynamic modulus of elasticity) of logs differed between families. The effects of growth rate on MFA and density differed between families and also between juvenile and mature wood. The faster growth rate in Nakatsu 3 appeared to improve wood properties and increase E _d of logs, although in many other families, faster growth rate had negative effects on desirable wood properties for structural use.     

An investigation on the transition characteristics of the wood cell walls during carbonization

The structural changes of the cell wall and crystalline cellulose of Quercus variabilis wood in a pyrolysis system at several temperatures ranging from 250 to 500°C were investigated to examine the wood carbonization characteristics. The volume of the wood sample was decreased and the weight loss was increased by increasing the carbonization temperature. Vessels collapsed severely in tangential direction during the charring process above 350°C. SEM observation indicated that the layering structure of the walls in wood fibers and parenchyma cells were retained below 300°C. However, the cell walls above 350°C changed to an amorphous-like structure without cell wall layering. X-ray diffraction confirmed that the cellulose crystalline substance was still remained at the carbonization temperature of 300°C but was not detected above 350°C. It can be concluded that the transition from Q. variabilis wood to charcoal might occur at approximately 350°C.     

New piezoelectric moduli of wood: <Emphasis Type="Italic">d</Emphasis><Subscript>31</Subscript> and <Emphasis Type="Italic">d</Emphasis><Subscript>32</Subscript>

This article reports the piezoelectric moduli of wood d ₃₁, d ₃₂, and d ₃₆. The piezoelectric moduli of wood d ₃₁ and d ₃₂ have not been previously reported, although there has been much research on the d ₁₄ and d ₂₅ moduli of wood. The moduli d ₃₁, d ₃₂, and d ₃₆ were measured carefully because their absolute values were considerably smaller than those of d ₁₄ and d ₂₅. For Softwoods, d ₃₆ values were mostly negative, whereas the values for hardwoods had either positive or negative values. The other moduli, d ₃₁ and d ₃₂, were a mixture of positive and negative values in softwoods and hardwoods. The existence of d ₃₁ and d ₃₂ suggests the presence of an electrical polarity of the cellulose crystal in the fiber direction of the wood. The polarities of d ₃₁ and d ₃₂ became clear from wood in the outer part of the trunk, where the crystallinity of cellulose is large and the alignment of the crystals becomes parallel to the fiber direction.     

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     

The effect of axial strain on crystalline cellulose in Norway spruce

The effect of strain on dry, clear Norway spruce (Picea abies [L.] Karst.) wood was studied by tensile testing along the cell axis and by in situ X-ray diffraction measurements. The mean microfibril angle (MFA) was initially 3–12 degrees and did not decrease due to strain. Based on the positions of the reflections 200 and 004 of crystalline cellulose, cellulose chains elongated and the distance between the hydrogen bonded sheets of chains decreased due to the strain. The elongation of the unit cell parallel to the cellulose chains was twice as high in juvenile wood as in mature wood. The (X-ray) Poisson ratio ν _ca for crystalline cellulose in Norway spruce was calculated from the deformation of the unit cell. The average ν _ca of earlywood was 0.28 ± 0.10 in juvenile wood and 0.38 ± 0.23 in mature wood. In latewood, the average ν _ca was 0.48 ± 0.10 in juvenile wood and 0.82 ± 0.11 in mature wood. The average ν _ca values were not directly correlated to the crystallite dimensions or to the mean MFA in juvenile and mature earlywood and latewood. The results show that the amorphous matrix has a definite effect on the deformation of cellulose crystallites.     

Comparative studies on microstructures and chemical compositions of cell walls of two solid wood floorings

Two common wood flooring materials, taun (Pometia spp.) and cumaru (Dipteryx odorata), were used as investigated objects and comparison was made between the two wood species for their density, microstructure, microfibril angle (MFA), cellulose crystallinity and the main chemical composition. Results showed that the density of cumaru was 0.941 g·cm^?3, significantly larger than that of taun, 0.737 g·cm^?3. The biggest difference of two wood species in microstructures was fiber cells. Fiber cells of cumaru had dense cell walls, almost no cell lumens; while fiber cells of taun had relatively thin cell walls, with apparent cell lumens. The thickness of fiber cell wall of cumaru and taun were 6.80 and 2.82 µm, respectively, and the former is about 2.5 times thicker than the latter. Measured data of MFA indicated that the average MFA of cumaru was 11.7°, smaller than that of taun, 13.4°. The relative crystallinity of cumaru and taun were 54.0 and 50.8%, respectively. The two wood species had the similar holocellulose contents, but the lignin content of cumaru was higher than that of taun, especially that the content of extractive of cumaru was as twice as that of taun.     

红松木倾斜角度对其木材形成组织的影响

为研究树干倾斜角度对应压木木材细胞壁形成过程的影响,以7年生红松苗木为研究对象,对其茎干进行不同角度的倾斜处理.先后测定苗木的树高和胸径、木材形成组织中的木质素和纤维素含量、傅里叶红外变化光谱和极性代谢产物.结果表明:倾斜角度对高生长的抑制作用非常显著,对直径生长无显著影响.倾斜后木质素含量增加,纤维素含量降低;倾斜角度对木质素和纤维素含量均有显著影响.不同倾斜角度FTIR吸收峰强度也有明显差异.糖类、脂类、氨基酸、含氮化合物、有机酸等代谢物随倾斜角度呈现不同的变化规律.因此,红松苗木50°倾斜处理形成典型的应压木结构.代谢物相对含量的变化规律与形成的木材宏观性质相吻合.代谢物的变化也反映了树木对应力刺激的响应机制.     

Measurement of cell wall penetration in wood of water-based chemicals using SEM/EDS and STEM/EDS technique

Summary The penetration of bulking chemicals (glycerol, PEG 200, PEG 1500 and pentaerythritol) into the cell wall of wood, Pinus sylvestris, has been studied. A number of different methods for determining the distribution of chemicals in the cell wall were used. Measurements of the increase in cell wall thickness showed that glycerol and PEG 200 resulted in greater cell wall bulking compared to PEG 1500 and pentaerythritol. Examination with SEM/EDS-linescan confirmed these results. However, the better resolution possible with the STEM/EDS-linescan revealed an inhomogenous distribution of the chemical in the cell wall. This is believed to be due to microcracks in the cell wall which are the result of the initial drying of the wood. This general damage to the cell wall could be the reason for the failure to find a stabilizing chemical and method. Received 10 February 1997     

Biological performance,water absorption,and swelling of wood treated with nano-particles combined with the application of Paraloid B72<Superscript>®</Superscript>

We evaluated fungal decay and mold resistance, leaching, and water absorption of nano-compounds and Paraloid B72^® (PB72) in treated wood specimens to develop new methods of consolidation by combining nano-particles and consolidants. Scots pine wood specimens were treated with dispersions of nano-CuO, nano-ZnO, nano-B₂O₃, nano-TiO₂, and nano-CeO₂. PB72 treatments of nano-particle-treated wood specimens were then carried out by either vacuum or immersion for 24 h. Previously, decayed wood specimens were also consolidated with the nano-compounds and PB72. PB72 treatments reduced element release from treated wood specimens. Nearly all nano-compounds + PB72 treatments increased the biological performance of treated wood specimens against decay fungi tested. PB72-only treated wood specimens had the highest weight losses in decay tests. No improvements were obtained in mold resistance tests when the nano-compounds and PB72 were combined. In nano-compound-only treatments, unleached specimens showed slightly lower water absorption values compared to untreated control specimens. Incorporation of PB72 into nano-compound-treated wood specimens resulted in considerably lower water absorption and volumetric swell. In previously decayed specimens treated with the nano-compounds and PB72 solution, water absorption after 2-h immersion declined compared to control specimens.     

The influence of thermal-hydro-mechanical processing on chemical characterization of Tsuga heterophylla

Viscoelastic thermal compression (VTC) is a type of thermal-hydro-mechanical (THM) processing that requires only a short processing time. THM processing causes some chemical transformations, the nature and extent of hydro-thermolysis depends on the special treatment conditions and the chemical nature of wood species. In the present study, the chemical transformations of the cell wall components and wood extractives during VTC treatment were investigated, and correlation between chemical characterizations and observed property changes was analyzed. For this purpose, the content of extractives and pH values were determined, and FTIR analysis was performed on extractable substances, extract-free wood, holocellulose, α-cellulose and lignin. Two temperatures and two steam exposure times were adopted to determine the influence of processing conditions on chemical characterization of Tsuga heterophylla. The results revealed that THM treatment caused a series of chemical reactions in extractives. Treatment temperature and conditioning time have significant influence on chemical changes of extractives. For all of the VTC treatments used in this study, no significant changes occurred in the lignin and α-cellulose components. The only significant chemical changes occurred in the hemicelluloses, which were primarily reduction of carbonyl and acetyl functional groups. This study also confirmed that the chemical transformation of wood correlates with property changes of VTC wood.     

Changes of crystallinity in wood cellulose by heat treatment under dried and moist conditions

The different effects of heat treatment on wood, especially on the cellulose crystallites of wood under ovendried and highly moist conditions, were investigated by X-ray diffractometer. Heat was found to increase significantly the crystallinity of wood cellulose; moreover, almost twice as much crystallization was observed after heat treatment of spruce and buna under a highly moist condition than under the oven-dried condition. In pure cellulose almost the same crystallization was observed under both the conditions, whereas more crystallization occurred in wood cellulose than in pure cellulose. Absolute crystallization was observed for the wood species and pure cellulose under both conditions, considering the thermal decomposition of the amorphous region in addition to crystallization. Our results suggested that other components accomparying wood cellulose were involved in the increase of crystallinity by heat treatment, and that wood cellulose contained more quasicrystalline regions than pure cellulose. Moreover, calculated apparent activation energies revealed that crystallization and decrystallization in pure and wood cellulose under heat treatment of highly moist condition were some-what easier than those under the oven-dried condition. The behavior of the piezoelectric modulusd ₂₅ almost paralleled that of crystallinity.