Characteristics of bamboo tissue in relation to cooling set

To clarify the effects of tissue and structure of bamboo on its bending properties and set by cooling (bent at 90°C and cooled to 20°C with bending), the effects of set in bast-fiber-rich (B_fib) and parenchyma-cell-rich (B_par) specimens were investigated with regard to their dynamic viscoelastic properties, chemical composition, and recovery from deformation with time. The results are summarized as follows: (1) while no clear effect of the proportion of parenchyma cells and bast fibers on residual set immediately after cooling was found, the relative recovery from the deformation with time for B_fib was larger than that for B_par. (2) Slightly higher lignin content and a-cellulose were seen in B_fib than in B_par. (3) The peak temperature of loss modulus (E″) found for B_par, which was attributable to micro-Brownian motion of lignin, was obviously lower than that for B_fib. This was considered to be due to differences in the degree of condensation of lignin or higher-order structure. From these results, it was deduced that the bastfiber-rich specimen, which showed a higher peak temperature regarding thermal softening of lignin allowing the induction of insufficient thermal-softening in the range of 20° to 90°C, caused a larger recovery from deformation with time. Part of this report was presented at the 56th Annual Meeting of the Japan Wood Research Society in Akita, August 2006     

Effects of temperature on mechano-sorptive creep of delignified wood

The effects of temperature on mechano-sorptive (MS) creep of delignified hinoki wood (Chamaecyparis obtusa Endl.) were investigated using longitudinal (L) and radial (R) specimens during adsorption and desorption over the temperature range of 20°–80°C. The results were compared with those of stepwise delignified specimens tested at a constant temperature of 20°C. It was found that the effects of temperature on the MS creep of delignified specimens are more remarkable than for untreated specimens. The tendencies of increasing MS creep with temperature, delignification, and their combination were observed. The increase in MS creep for L specimens was relatively small and almost equal in both adsorption and desorption processes, while for R specimens the MS creep was small in desorption, but significantly different in adsorption. In addition, good correlation was observed between the MS coefficient (K) and instantaneous compliance (J ₀). The increase in MS creep occurs as a result of temperature increase or decrease in lignin content, or their interacting effects. However, in the case of desorption for R specimens, the increase of MS creep was unexpectedly small due to a remarkably increased J ₀. Part of this report was presented at the 15th Annual Meeting of the Chubu Branch of the Japan Wood Research Society in Fukui, October 2005     

Dynamic viscoelastic behavior of wood under drying conditions

In this study heartwood from a Chinese fir [Cunninghamia lanceolata (Lamb.) Hook] plantation was treated using a high-temperature drying (HTD) method at 115°C, a low-temperature drying (LTD) method at 65°C, and freeze vacuum drying (FVD), respectively. The dynamic viscoelastic properties of dried wood specimens were investigated. The measurements were carried out at a temperature range of −120 to 250°C at four different frequencies (1, 2, 5, and 10 Hz) using dynamic mechanical analysis (DMA). We have drawn the following conclusions: 1) the storage modulus E′ and loss modulus E″ are the highest for HTD wood and the lowest for FVD wood; 2) three relaxation processes were detected in HTD and LTD wood, attributed to the micro-Brownian motion of cell wall polymers in the non-crystalline region, the oscillations of the torso of cell wall polymers, and the motions of the methyl groups of cell wall polymers in the non-crystalline region in a decreasing order of temperatures at which they occurred; and 3) in FVD wood, four relaxation processes were observed. A newly added relaxation is attributed to the micro-Brownian motions of lignin molecules. This study suggests that both the HTD and the LTD methods restrict the micro-Brownian motion of lignin molecules somewhat by the cross-linking of chains due to their heating history. __________ Translated from Journal of Beijing Forestry University, 2008, 30(3): 96–100 [译自: 北京林业大学学报]     

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.     

Modeling of sapwood and heartwood delignification kinetics of <Emphasis Type="Italic">Eucalyptus globulus</Emphasis> using consecutive and simultaneous approaches

Eucalyptus globulus sapwood and heartwood were delignified at 130°, 150°, or 170°C by kraft pulping. Pulp yields of heartwood were lower than those of sapwood (46.5% vs. 50.4% at 170°C). Delignification was modeled using consecutive and simultaneous kinetic models. The modeling was similar for heartwood and sapwood, and either approach could be used, with both yielding good correlations between experimental and model data. The consecutive model identified two delignification phases with similar reaction rates and activation energies for heartwood and sapwood at 150° and 170°C. At 130°C only one phase was identified. Three reactive types of lignin fractions were identified using the simultaneous model, without differences between heartwood and sapwood. Their reaction rates were 0.152, 0.138, and 0.003 min⁻¹ at 170°C, and the activation energies were 132, 119, and 102 kJ.mol⁻¹. The presence of heartwood did not influence the kinetic development of delignification. The negative impact of heartwood in pulping is related to the higher content of extractives (9.8% vs. 3.9% in heartwood and sapwood) and to their influence on the process, namely in the heating-totemperature phase when a substantial mass loss occurs (30% vs. 20% for heartwood and sapwood).     

Thermal-softening properties and cooling set of water-saturated bamboo within proportional limit

Thermal-softening properties and cooling set of water-saturated bamboo were investigated using stressrelaxation measurements in heating and cooling processes, followed by residual deflection measurement. In the heating process, an obvious decrease in relative relaxation modulus due to thermal-softening of lignin was found at around 60°C. On the other hand, no clear change in the relative relaxation modulus was recognized in the cooling process. After the cooling process, about 65% and 75% of residual set was measured when the specimen was loaded on the epidermis and endodermis side, respectively. Also, residual set depended on the maximum temperature reached in the heating process and the unloaded temperature in the cooling process. From these results, it was deduced that the glass transition of lignin from the rubbery to glassy state is important to fix the deformation. Comparing thermal-softening behavior between bamboo and wood, the relative relaxation modulus of wood decreased steeply at higher temperatures than for bamboo. On the other hand, while about 75% of residual set was also found for wood, almost the same as for bamboo, the recovery of deformation with time was larger for wood than for bamboo. Part of this article was presented at the 53rd Annual Meeting of the Japan Zairyou Society, Okayama, May 2004     

Characteristic fragment ions from lignin and polysaccharides in ToF–SIMS

Different model compounds for lignin, hemicelluloses and pectins were studied by time-of-flight secondary-ion mass spectrometry (ToF–SIMS). Mass spectra of Klason lignin from normal and compression spruce wood, aspen wood and wheat straw were compared. Spectra of brominated spruce and aspen wood sections showed fragment ions attributed to brominated guaiacyl and syringyl units in lignin at m/z 215, 217, 229 and 231, and m/z 245, 247, 249 and 261, respectively. Spectra of mono-, oligo- and polysaccharides showed fragment ions at m/z 127 and 145 characteristic for hexose units, and ions at m/z 115 and 133 characteristic for pentose units. The same ions were detected in spectra of delignified spruce and aspen wood sections. Labelling of anionic groups by Sr²⁺ ions followed by ToF–SIMS analysis showed that pectins were present at specific locations on the surfaces of spruce and aspen wood sections still after delignification with hydrogen peroxide in acetic acid.     

Vibrational properties of wetwood of todomatsu (<Emphasis Type="Italic">Abies sachalinensis</Emphasis>) at high temperature

The object of this study was to understand precisely the drying characteristics of wetwood of todomatsu (Abies sachalinensis Mast.). For this purpose, the vibrational properties of wetwood of todomatsu at high temperature were compared with those of normal parts that had lower green moisture content than the wetwood. Specimens were cut respectively from the wetwood and normal parts, and matched in the radial direction. The specimens and the measuring systems were placed in an electric drying oven and free-free vibration tests were conducted in the oven under absolutely dry conditions. The wetwood and the normal parts were tested separately. The temperature was raised from room temperature to 200°C and then lowered to 50°C in steps of 25°C. The specific Young’s modulus decreased with an increase in temperature during the heating process while it increased with the decreasing temperature during the cooling process. There was no significant difference in the specific Young’s modulus between the wetwood and the normal part at all tested temperatures. The loss tangent took a minimum value at about 100°C in both the heating and cooling processes. There was no significant difference in the loss tangent between the wetwood and the normal part. Thus, the elastic and viscoelastic behaviors of the wetwood appear to be similar to those of the normal part in the temperature range of an actual kiln-drying process.     

Mechanical properties of wood in an unstable state due to temperature changes,and analysis of the relevant mechanism VI: dielectric relaxation of quenched wood

To analyze the effects of lignin on the destabilization of wood due to quenching, we examined the dielectric properties of untreated and delignified wood before and after quenching at 20°C from 50 Hz to 100 MHz. For untreated wood, the inflection points of log ε′ and log σ vs log f and the peak of log(tan δ) vs log f were attributed to interfacial polarization before quenching, and the location of the inflection point shifted to a higher frequency with increasing moisture content because of changes in the water cluster. After quenching, the inflection points of log ε′ and log σ and the peak of log(tan δ ) shifted to higher frequency; however, the values of log ε′, log σ recovered to those before quenching with the passage of time. For delignified wood, dielectric relaxation was observed at a higher frequency than for untreated wood irrespective of quenching. It was inferred that the mobility of water molecules was influenced by the cluster surroundings because of increased number of adsorption sites in hemicellulose. Moreover, after quenching, the recovery process did not change greatly over time; it was shown that the matrix structure was affected more by quenching with the loss of lignin.     

A mathematical model of kraft pulping related to the alkali concentration in the cooking liquor

Summary A new mathematical model for checking and controlling the kraft pulping process has been derived. The model is based on the modified relationship between the lignin content and the alkali concentration of a cooking liquor expressed as the ratio of lignin/active alkali vs. concentration of the active alkali in a cooking liquor. The derived model characterizes the variation of the lignin content of the partially delignified wood or pulp with the concentration of the residual alkali in a cooking liquor during an entire pulping cycle, i.e. during the initial, transition, bulk and residual phases of the kraft delignification. The relationship between the lignin content of the partially delignified wood ships or pulp and the concentration of the residual alkali in a cooking liquor is expressed by the logarithmic straight line equation or its power form. The slope and intercept constants of the derived equation for the individual phase of delignification have different values. Received 5 June 1996     

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

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

Cellular UV-microspectrophotometric investigations on pine wood ( Pinus taeda and Pinus elliottii) delignification during biopulping with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. and alkaline sulfite/anthraquinone tr

Scanning UV-microspectrophotometry was used to investigate the topochemistry of lignin removal from pine wood (Pinus taeda and P. elliottii) chips during biopulping involving wood treatment with Ceriporiopsis subvermispora (Pilát) Gilbn. & Ryv. followed by alkaline sulfite/anthraquinone delignification. A delignification front starting from the lumen towards the compound middle lamella was clearly observed in micrographs recorded from individual cell wall layers of wood samples biotreated for 30 days. Lignin was removed without cell wall erosion. UV-micrographs of wood samples cooked for a short time (90 min pulping) showed that the S2 of biotreated samples are more homogeneously delignified compared to the S2 of the undecayed controls. Similarly, the compound middle lamella and cell corners are also more delignified in biotreated samples. On the other hand, UV-micrographs of samples cooked for a long time (150 min pulping at 170°C) showed that there are no significant differences in the contents of residual lignin retained in the S2 of undecayed and biotreated wood samples.     

The influence of acetosolv pulping conditions on the enzymatic hydrolysis of Eucalyptus pulps

Eucalyptus globulus wood was subjected first to HCl–catalysed delignification with 70% acetic acid under conditions realizing an incomplete 3 × 3 × 3 factorial design (HCl concentration 0, 0.025 or 0.05%; temperature 120, 140 or 160 °C; reaction time 1, 2.5 or 4 h), and then to enzymatic hydrolysis. The hydrolysis kinetics conformed to both Ghose's empirical model and a biexponential equation. The biexponential fit implies the presence of both readily and reluctantly hydrolysed cellulose fractions, and the fitted coefficients show hydrolysis yield to depend largely on the digestibility of the latter. Multiple regression of performance variables on pulping conditions showed that neither the rate nor the extent of hydrolysis is greatest for pulps with minimum lignin or xylose contents; we attribute this circumstance to the condensation and precipitation of lignin under severe pulping conditions, which protects the cellulose of the pulp from enzymatic attack. Received 20 June 1998     

Mechanical properties of wood in an unstable state due to temperature changes,and analysis of the relevant mechanism IV: effect of chemical components on destabilization of wood

In order to investigate the effects of chemical components and matrix structure on the destabilization of quenched wood, we examined the physical and mechanical properties of steam-treated wood, hemicellulose-extracted wood, and delignified wood, which were treated at different levels. For steam-treated and hemicellulose-extracted wood,the relative relaxation modulus of the quenched sample was lower than that of the respective control sample. For delignified wood, the relative relaxation modulus fell with weight loss and reached a minimum value at a certain weight loss, and subsequently increased significantly. The hygroscopicity of all treated samples changed slightly by steaming, whereas increased with removing the component. More-over, the average volumetric swelling per 1% MC at 100% relative humidity (RH) was less than at 75% RH and 93% RH for component-removed wood. It was clear that a void structure existed. As a result, the destabilization evaluated by the fluidity (1 - E _t/E ₀) of steam-treated wood was influenced by the amount of adsorbed water. For component-removed wood, destabilization increased temporarily at lower weight loss because of nonuniform cohesive structure. At high weight loss, destabilization will decreased because capillary-condensed water gathered in the voids and obstructed the motion of adsorbed water. However, the destabilization of all treated wood changed less than that of chemically modified wood.     

Changes in structural and chemical components of wood delignified by fungi

Summary Cerrena unicolor, Ganoderma applanatum, Ischnoderma resinosum and Poria medulla-panis were associated with birch wood that had been selectively delignified in the forest. Preferential lignin degradation was not uniformly distributed throughout the decayed wood. A typical white rot causing a simultaneous removal of all cell wall components was also present. In the delignified wood, 95 to 98% of the lignin was removed as well as substantial amounts of hemicelluloses. Scanning and transmission electron microscopy were used to identify the micromorphological and ultrastructural changes that occurred in the cells during degradation. In delignified areas the compound middle lamella was extensively degraded causing a defibration of cells. The secondary wall, especially the S₂ layer, remained relatively unaltered. In simultaneously white-rotted wood all cell wall layers were progressively removed from the lumen toward the middle lamella causing erosion troughs or holes to form. Large voids filled with fungal mycelia resulted from a coalition of degraded areas. Birch wood decayed in laboratory soil-block tests was also intermittently delignified. Selective delignification, sparsely distributed throughout the wood, and a simultaneous rot resulting in the removal of all cell wall components were evident. Scanning electron microscopy appears to be an efficient technique for examining decayed wood for fungi with the capacity to selectively delignify wood.The authors would like to thank Kathy Zuzek for technical assistance and Dr. M. Larsen, Forest Prod. Lab., Madison, for identifying the sporophores of Poria medulla-panis. This research was founded in part by a grant from the USDA Forest Service, Forest Products Laboratory and from the Graduate School, University of Minnesota     

Comparison of transverse compression creep of Pseudotsuga menziesii and Populus sp. in high-temperature steam environments

Compression creep experiments of Douglas-fir wood (Pseudotsuga menziesii) were performed at high temperature (150°C, 160°C, and 170°C) and under various conditions of steam pressure. The results established that environment conditions had a significant effect on compressive deformation, with the largest deformation obtained under saturated steam conditions. While the temperature significantly affected the compressive deformation of specimens under transient conditions, the temperature within the range studied had little effect on the compressive deformation in saturated steam. Furthermore, in specimens compressed under superheated and transient steam conditions, primary creep behavior was exhibited; while in specimens compressed under saturated steam conditions, creep deformation appeared to enter directly into secondary creep. Moreover, in saturated steam specimens very little creep was observed due to high initial deformation and little potential for additional cell wall buckling. The compressive creep measurements of Douglas-fir were compared with compressive creep of hybrid poplar (Populus deltoides × Populus trichocarpa). Due to lower initial density, and perhaps smaller microfiber angle and lower lignin content of tension wood, the compressive creep modulus of hybrid poplar was lower than Douglas-fir. Therefore, compressive deformation of Douglas-fir, at nearly all examined steam conditions and temperatures, was smaller than compressive deformation of hybrid poplar.     

Thermochemical behavior of Norway spruce (Picea abies) at 180–225 °C

Norway spruce (Picea abies) was heated for 2–8 h in the temperature range 180–225 °C, under a steam atmosphere. The chemical analyses of the treated feedstock samples indicated that during heating (total mass loss 1.5–12.5% of the initial DS) carbohydrates (hemicelluloses and cellulose) were clearly more amenable to various degradation reactions than lignin. In addition, major water-soluble products released from the feedstock material during the treatments were classified into several compound groups and changes in the relative mass portion of these groups were monitored by GC during a separate experiment. Received 20 December 1998     

A novel method of acetylation of wood using supercritical carbon dioxide

Sugi heartwood was acetylated with acetic anhydride in supercritical carbon dioxide (CO₂) (120°C or 130°C, 10–12 MPa). As a result, the weight percent gain increased with increasing acetylation time up to 16%–20% at 1 h and 24%–28% at 24 h. The antiswelling efficiency of the acetylated specimens reached 75%–80% at 3–4 h of acetylation. It is supposed that the acetylation in supercritical CO₂ has a high bulking effect compared with liquid-phase and vapor-phase acetylation with uncatalyzed acetic anhydride. The results showed that the acetylation progressed rapidly because supercritical CO₂ and acetic anhydride formed a single phase at more than 90°C, and the acetic anhydride reached the reaction sites in the wood quickly.     

Nondestructive evaluation of heat-treated Eucalyptus grandis Hill ex Maiden wood using stress wave method

The objectives of this study were to evaluate the effect of heat treatment of eucalypt wood (Eucalyptus grandis Hill ex Maiden) on the dynamic modulus of elasticity by using the stress wave nondestructive method and also to determine the air-dry density variation, weight loss and equilibrium moisture content following treatment. Heat treatments were performed at four different temperatures (180, 200, 215 and 230°C) and for three different durations (15?min, 2 and 4?h). The results revealed a significant reduction in air-dry density following heat treatment independent of temperature and time. A significant weight loss was observed between and within treatments. The treatment at 230°C for 2 and 4?h produced a weight loss of 20.5 and 26.5%, respectively, which was statistically different from other treatment conditions. The dynamic modulus of elasticity decreased by about 13% in the most severe treatment (230°C for 4?h). Depending on the temperature and time, the equilibrium moisture content was significantly reduced within the range of 40–74%.     

Polyelectrolyte swelling behavior of chlorite delignified spruce wood fibers

Summary A coarse thermomechanical Asplund pulp was prepared from Norway spruce (Picea abies). The pulp was delignified to different degrees using acidified sodium chlorite. The swelling behavior (measured as water retention value=WRV) of the resulting pulps was studied under various chemical conditions (pH and conc. of NaCl). It is shown that chlorite-delignified pulps have an appreciable polyelectrolytic character. Whereas the WRV of an Asplund pulp does not respond to changes in the chemical environment, the delignified pulp has a WRV of 155 at pH 3 and 250 at pH 9. Compared under the same chemical conditions, the WRV increases with increasing degree of delignification (<70%) and is approximately constant at high degrees of delignification (>70%).The authors are indebted to Mr. Claes Beer at Sund-Defibrator, who assisted with the preparation of the Asplund pulp