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 anisotropic swelling and shrinking process of wood

To elucidate the origin of the shrinking anisotropy of wood during the drying process, as well as to begin to gain an understanding of the interaction between the moisture and the cell wall components, the shrinking process of a single wood fiber regarding water desorption was simulated by using an analytical model which was developed in the previous report (Part 1). Resulting data were compared with the experimental ones in this paper. The following conclusions were obtained: (1) The matrix substance, as a skeleton in the secondary wall, tends to shrink isotropically. However, the cellulose microfibrils, as a rigid framework of the cell wall, almost did not shrink at all due to the water desorption. As result, wood shrinks anisotropically during a drying process. The microfibril angle in the S2 layer is one of the most important factors related to the degree of shrinking anisotropy of the wood while drying. (2) According to the simulation, the expansive strain caused in the matrix skeleton by the water sorption increases by 15% (= 150,000 micro-strains) from the oven-dried condition to the green condition. Based on this value, the moisture content at the fiber saturation point is calculated to be about 35%, which is close to the experimentally obtained one. These results give quantitative evidences that the hygroexpansion of the wood cell wall is controlled by the mechanism of the reinforced matrix hypothesis. Received: 28 July 1998     

Change in mechanical interaction between cellulose microfibril and matrix substance in wood cell wall induced by hygrothermal treatment

To investigate in detail the mechanical interactions and associations between cellulose microfibrils (CMFs) and the matrix substance, we measured the dimensional changes in cellulose crystals in wood cell walls after different treatments. The transverse expansion of CMFs observed after hygrothermal treatment and subsequent drying suggests that the matrix substance compresses the CMFs transversely under green conditions. However, as heat treatment breaks or weakens the association of the CMFs and the matrix substance, under hygrothermal treatment and drying at high temperature the matrix substance cannot compress the CMFs in the direction of the chain.     

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.     

In situ measurement of tensile elastic moduli of individual component polymers with a 3D assembly mode in wood cell walls

We attempted to measure in situ the tensile elastic moduli of individual component polymers with a three-dimensional (3D) assembly mode in the cell walls of Sugi (Cryptomeria japonica D. Don) without isolating the polymers. To prepare wood tangential slices [50 × 6 × 0.2 mm (L × T × R)] consisting of lignin with a 3D assembly mode in the cell walls, cellulose and hemicellulose were removed using the method of Terashima and Yoshida (2006) to obtain methylated periodate lignin slices. To prepare wood slices consisting of polysaccharide with a 3D assembly mode in the cell walls, lignin was removed using the method of Maekawa and Koshijima (1983) to obtain holocellulose slices. Static tensile test was applied to determine the elastic moduli of 3D lignin and 3D polysaccharide slices. The followings were revealed. The elastic modulus of the 3D lignin slices was 2.8 GPa, regardless of the microfibril angle (MFA) in the slices. The elastic moduli of the 3D polysaccharide slices with MFAs of 14°, 23°, 34°, and 42° were 18, 12, 9, and 4 GPa, respectively. The former shows that the lignin with a 3D assembly mode behaves as an isotropic substance in the cell walls, while the latter suggests that the 3D polysaccharide slice shows marked anisotropic structure in the cell wall. Despite the fact that cellulose content increased after lignin removal, values of substantial elastic modulus of the cell wall slightly decreased regardless of MFA. Following two possible reasons were pointed out for explaining this phenomenon. First, lignin removal caused an artifactual deterioration in the polysaccharide slices at the level of macromolecular aggregate. Second, rigid and fusiform-shaped cellulose crystallites are dispersed in the soft matrix of amorphous polysaccharide, and those are loosely connected to each other by the intermediary of matrix polysaccharide. Those suggest that the rigid cellulose crystallite can optimize its strong mechanical performance in the polysaccharide framework of the wood cell wall in combination with the ligninification.     

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.     

Mechanical constraints on lignin deposition during lignification

Summary The ultrastructure of lignifying cell walls in Pinus radiata D.Don was investigated using potassium permanganate staining and transmission electron microscopy. Lignin deposition occurred at numerous discrete sites within various cell wall regions, suggesting the presence of some initiating agent at these sites. In the middle lamella region, lignin deposition occurred by addition of protolignin monomers to spherical particles of lignin. Lignification was completed by expansion of these spherical particles, initially forming irregular patterns of lignification followed by infilling of adjacent areas. In contrast, lignification in the secondary wall occurred by deposition of protolignin monomers onto the ends of expanding lignin lamellae between cellulose microfibrils leading to greatly elongated patches of lignin due to the greater rate of deposition along the microfibril axis compared to that across it. It is concluded that the cellulose matrix in which lignin deposition occurs, in the secondary wall, can exert a mechanical influence which limits the rate of lignin deposition in the direction perpendicular to the microfibril axis.     

Growth stress generation: a new mechanical model of the dimensional change of wood cells during maturation

A new mechanical model was developed to introduce the maturation process of wood cells theoretically. Using mechanical and physical properties of the two components of the cell wall, namely, a matrix reinforced by oriented cellulose microfibrils, it is possible to predict the relation between the anisotropic released strains and the microfibril angle. The model used in this study is based on the unified hypothesis combining the compressive stress generated in the cell wall matrix and the tensile stress originating in the cellulose microfibril as a framework. It is simple compared to the previously derived multilayered model, but it does not strictly fulfill all conditions of static equilibrium. Nevertheless, an excellent fit with observations can be obtained through varying a limited number of parameters.     

Role of the gelatinous layer on the origin of the physical properties of the tension wood

To discuss the role of the gelatinous layer (G-layer) on the origins of the physical properties peculiar to the tension wood fiber (TW fiber), the deformation process of an isolated TW fiber caused by a certain biomechanical state change was formulated mathematically. The mechanical model used in the present formulation is a four-layered hollow cylinder having the compound middle lamella (CML), the outer layer of the secondary wall (S1) and its middle layer (S2), and the G-layer (G) as an innermost layer. In the formulation, the reinforced matrix mechanism was applied to represent the mechanical interaction between the cellulose microfibril (CMF) as a framework bundle and the amorphous substance as a matrix skeleton in each layer. The model formulated in the present study is thought to be useful to investigate the origins of extensive longitudinal drying shrinkage, large tensile growth stress, and a high axial elastic modulus, which are rheological properties peculiar to the TW. In this article, the detailed process of the mathematical formulation is described. In a subsequent article, some TW properties from a 70-year-old Kohauchiwakaede (Acer sieboldianum Miq.) will be analyzed using the newly developed model.     

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.     

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.     

Anatomy and lignin distribution of reaction wood in two Magnolia species

Summary Anatomical features of reaction wood formed in two Magnolia species, M. obovata Thunb. and M. kobus DC. which are considered to be among the primitive angiosperms, were observed. In addition, the distribution of guaiacyl and syringyl units of lignins in the cell walls of normal and reaction wood was examined using ultraviolet (UV)- and visible light (VL)- microspectrophotometry coupled with the Wiesner and M?ule reactions. The two Magnolia species formed a tension-like reaction wood without possessing the typical gelatinous layer (G-layer) on the upper side of the inclined stem or branch, in which a radial growth promotion occurred. Compared with the normal wood, the reaction wood had the following anatomical features: (1) the secondary walls of fiber tracheids lacked the S₃ layer, (2) the innermost layer of fiber-tracheid walls showed a small microfibril angle, a fact being similar to the orientation of the microfibril angle of the G-layer in tension wood, and (3) the amounts of lignin decreased in the cell walls of fiber tracheids, especially with great decrease in proportion of guaiacyl units in lignins. In addition, VL-microspectrophotometry coupled with the Wiesner and M?ule reactions adopted in the present study showed potential to estimate the lignin contents in the cell walls and the proportion of guaiacyl and syringyl units in lignins. Received: 15 July 1998     

Theory of X-ray measurement of microfibril angle in wood

Summary The property of fibre symmetry as exhibited by wood cellulose can be used to derive an explicit relationship between the orientation of a cellulose microfibril and the orientation of the X-ray beam diffracted by any of its crystallographic planes. The solution applies to a microfibril of any orientation and so is well suited to evaluating the microfibril angle distribution in wood containing cells of any cross-sectional shape. The (002) and (040) reflections of cellulose have complementary properties that could be exploited to enable current problems associated with the use of each individually for evaluating the mean microfibril angle of the S2 layer to be overcome. It is expected that it will be possible to measure the microfibril angle distribution throughout the whole cell wall and also measure the average cell cross-section of a wood sample, by analysing (002) and (040) diffraction profiles in conjunction with each other.This work is supported by the NZ Foundation for Research, Science and Technology under contract # UOC 401     

Helical fissures in compression wood cells: Causative factors and mechanics of development

Summary There is evidence showing that lignification causes both an increase in the thickness of the walls, and changes in the overall width or circumference of wood cells. Although data are not available on changes in length during lignification, it can be deduced that these must also tend to occur. As lignin occupies sites in the cell walls corresponding to those occupied by water, the theory of anisotropic shrinkage of wood may be used to predict the proportional dimensional changes tending to occur as each wall layer in a compression wood cell is lignified. Taking account of the microfibril angles in those layers, it is shown that if the angle for S₂ is more than about 45°, inevitably S₂ will tend to develop deep helical fissures or splits of the form of those reported in the literature.     

Creep and stress relaxation behavior for natural cellulose crystal of wood cell wall under uniaxial tensile stress in the fiber direction

We investigated the temporal changes in creep and stress relaxation behavior in both microscopic crystalline cellulose and macroscopic strain of wood specimen using Japanese cypress (Chamaecyparis obtusa Endl.) to understand the viscoelastic properties of wood cell walls. Specimens 600 µm in thickness were observed by the X-ray diffraction and submitted to tensile load. The crystal lattice strain of (004) plane and macroscopic strain of specimen were continuously detected during creep and stress relaxation tests. It was found that the creep compliance based on macroscopic strain showed a gradual increase after instantaneous deformation due to loading and then the parts of creep deformation remained as permanent strain after unloading. On the other hand, crystal lattice strain showed a different behavior for macroscopic strain; it kept a constant value after instantaneous deformation due to loading and then increased gradually after a certain period of time. These differences between macroscopic and microscopic levels were never found in the stress relaxation tests in this study. Relaxation modulus at the macroscopic level only showed a decreasing trend throughout the relaxation process. However crystal lattice strain kept a constant value during the macroscopic relaxation process. In addition, the microfibril angle (MFA) of wood cell wall has a role of mechanical behavior at microscopic level; crystal lattice strains were smaller with increasing MFA at both creep and relaxation processes. Creep compliance and stress relaxation modulus at the macroscopic level decreased and increased with increasing MFA, respectively. Our results on the viscoelastic behavior at microscopic level evidenced its dependency on MFA.     

Reaction wood anatomy and lignin distribution in <Emphasis Type="Italic">Gnetum gnemon</Emphasis> branches

This study investigated the anatomical and chemical characteristics of the reaction wood of a gymnpsperm species, Gnetum gnemon, and discussed on contributing factor for the type of reaction wood in this species. Cell morphology, microfibril angle (MFA) of the S₂ layer and lignin distribution in secondary walls of tracheary elements, and lignin content were examined on three branches. Observations included no G-layer formation, significant decreases in vessel frequency, and altered MFA, and visible-light absorbance after lignin colour reactions in tracheid and fiber tracheid walls on the upper side in almost all samples. These results suggest that reaction wood in G. gnemon was similar to that in ‘tension-wood-like-reaction wood’ in angiosperms. On the other hand, reaction wood showed decrease in the lignin concentration in the fiber tracheid walls compared to the tracheid walls. In addition, the lignin in the tracheid and fiber tracheid walls was originally rich in syringyl units, suggesting that changes in the anatomical and chemical characteristics of secondary xylem due to reaction wood formation might relate to the ratio of the syringyl to guaiacyl units in lignin in the cell walls which function for mechanical support.     

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.     

Microfibril angle variability in Masson Pine (Pinus massoniana Lamb.) using X-ray diffraction

The microfibril angle of fiber walls is an ultra-microscopic feature affecting the performance of wood products. It is there-fore essential to get more definitive information to improve selection and utilization. X-ray diffraction is a rapid method for measur-ing microfibril angles. In this paper, the variability of microfibril angle in plantation-grown Masson pine was investigated by peak-fitting method. This method was compared with the traditional hand-drawn method, 40% peak height method and half peak h...     

Wood nanocelluloses: fundamentals and applications as new bio-based nanomaterials

Nanocelluloses, which include nanofibrillated celluloses (NFCs) and cellulose nanocrystals (CNCs) with high and low aspect ratios, respectively, are promising new bio-based nanomaterials, prepared from wood and other plant celluloses by mechanical shearing in water with or without pretreatments. Low degrees of enzymatic hydrolysis, carboxymethylation, acetylation, oxidation, and other position-selective modifications on cellulose microfibril surfaces have been applied as pretreatments to wood celluloses to reduce energy consumption in the mechanical shearing process and to improve the nanofibrillation level of the obtained NFCs. NFCs are convertible to nanocellulose sheets, films, hydrogels, foams, and aerogels with fibril network structures or close-packing structures using coating on base films or filtration process like papermaking, which is advantageous for efficient removal of water predominantly present in the NFC/water dispersions. NFC-containing self-standing films, coated films, and NFC/matrix nanocomposites in most cases show explicitly high mechanical strength and ductility despite being lightweight and having optical transparency, thermal stability, and gas-barrier properties. Because NFCs have aspect ratios and molecular weights higher than those of CNCs, the most promising and challenging end products are NFC-containing nanocomposite materials having higher functionalities than those of the conventional fiber-reinforced composite materials.     

Dynamic water vapour sorption properties of wood treated with glutaraldehyde

The dynamic water vapour sorption properties of Scots pine (Pinus sylvestris L.) wood samples were studied to investigate the modifying effects of glutaraldehyde. Pine sapwood was treated with solutions of glutaraldehyde and a catalyst (magnesium chloride) to obtain weight per cent gains of 0.5, 8.6, 15.5, and 21.0%, respectively. The sorption behaviour of untreated and treated wood was measured using a Dynamic Vapour Sorption apparatus. The results showed considerable reduction in equilibrium moisture content of wood and the corresponding equilibrium time at each target relative humidity (RH) due to glutaraldehyde treatment. The moisture adsorption and desorption rates of modified and unmodified wood were generally faster in the low RH range (up to approximate 20%) than in the high range. Modification primarily reduced the adsorption and desorption rates over the high RH range of 20–95%. Glutaraldehyde modification resulted in a reduction in sorption hysteresis due to the loss of elasticity of cell walls.