Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin I: effects of pressing pressure and pressure holding

The deformation behavior of low molecular weight phenol formaldehyde (PF) resin-impregnated wood under compression in the radial direction was investigated for obtaining high-strength wood at low pressing pressures. Flat-sawn grain Japanese cedar (Cryptomeria japonica) blocks with a density of 0.34g/cm³ were treated with aqueous solution of 20% low molecular weight PF resin resulting in weight gain of 60.8%. Oven-dried specimens were compressed using hot plates fixed to a testing machine. The temperature was 150°C and the pressing speed was 5mm/min. The impregnation of PF resin caused significant softening of the cell walls resulting in collapse at low pressures. The cell wall collapse was strain-dependent and occurred at a strain of 0.05–0.06mm/mm regardless of whether the wood was treated with PF resin. Thus, pressure holding causing creep deformation of the cell walls was also effective in initiating cell wall collapse at low pressure. Utilizing a combination of low molecular weight PF resin impregnation and pressure holding at 2MPa resulted in a density increase of PF resin-treated wood from 0.45 to 1.1g/cm³. At the same time, the Youngs modulus and bending strength increased from 10GPa to 22GPa and 80MPa to 250MPa, respectively. It can be concluded that effective utilization of the collapse region of the cell wall is a desirable method for obtaining high-strength PF resin-impregnated wood at low pressing pressures.     

Structure of cellulose microfibrils and the hydration effect in <Emphasis Type="Italic">Cryptomeria japonica</Emphasis>: a small-angle X-ray scattering study

The nanometer scale structure of cell walls in sugi wood (Cryptomeria japonica D. Don) and the hydration dependence were examined by the small angle X-ray scattering technique. Disk-shaped scattering patterns were observed for sugi wood. The radial average of two-dimensional data from the cross section could supply the scattering intensity with statistical accuracy much higher than that obtained from the sector average of the streak-shaped scattering pattern, and both the scattering intensities provided similar structural information. The scattering patterns from the cross section of the wood are characterized by rhombic or cross-shaped isointensity curves for the lower q region and by circularly symmetric isointensity curves for the higher q region. This shows that the disk-shaped scattering has two different kinds of scattering origins. The microfibril radii in the cell wall were determined by fitting the model scattering function of cylindrical fibrils to the scattering data. Values of 12.3 ± 0.3 and 12.2 ± 0.3 were obtained for the fibril radii of the neighboring earlywood and latewood, respectively, in dry specimens. A drastic structural change of the cell walls was detected with increasing water content from 40% to 100%. A low q rise in the scattering intensities below 0.1^–1 became weak and changed into a flat pattern, and the rhombic isointensity curves changed to cross-shaped patterns in the two-dimensional scattering from the cross section. The calculated radii R increased from 12.2 ± 0.3 to 13.3 ± 0.1.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002     

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.     

Dependence of reaction kinetics and physical and mechanical properties on the reaction systems of acetylation II: physical and mechanical properties

Acetylation of wood was carried out in acetic anhydride only, acetic anhydride/xylene 1:1 (v/v), and acetic anhydride/pyridine 4:1 (v/v) solutions. The antishrink efficiency (ASE), hygroscopic properties, vibrational properties, and bending strength were compared among the three reaction solutions. The ASE was a simple function of weight gain (WG); the equilibrium moisture content at a given WG differed among the reaction solutions. Based on this fact and the results of repeated water soaking and oven-drying tests, it was found that the bulking effect was a major factor, and that decreased hygroscopicity contributes only slightly to the dimensional stabilization by acetylation. The difference in equilibrium moisture content among reaction solutions appears more significant in block samples than wood meal, probably due to the fiber-to-fiber bonds in the former. The tendencies for change in the specific Youngs modulus and the loss tangent differed among reaction solutions, whereas in the static bending test the difference was not marked.Part of this report was represented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Plastic deformation in small clear pieces of Scots pine (<Emphasis Type="Italic">Pinus sylvestris</Emphasis>) during densification with the CaLignum process

Specimens made of clear wood from Scots pine (Pinus sylvestris L.) were compressed semi-isostatically at 25°C in a Quintus press. Pressure ranged from 0 to 140MPa and the maximum decrease in the crosscut area was about 60%. Quarter-sawn and plain-sawn specimens were densified with the inside face (pith side) up or down. A laser-made dot grid on the crosscut area of the uncompressed specimen was used to calculate plastic strains by image analysis of the displacement of dots after compression. Multivariate models were developed to determine the causes of deformation. The lower face was restrained by the press table and remained flat whereas sides attached to the rubber diaphragm became more irregularly shaped when compressed. Most of the total compression occurred below 50MPa and was determined exclusively by pressure. Above 50MPa, wood density was more important and compression was lower in the interior of specimens and in heartwood. Plastic compressive strain occurred predominately in the radial direction and toward the rigid press table. Strains were dependent on the sawing pattern and orientation. The growth rings of quarter-sawn specimens oriented with the outer face (bark side) down tended to buckle.     

Specific detection of a basidiomycete, Phlebia brevispora associated with butt rot of Chamaecyparis obtusa, by PCR-based analysis

In order to monitor the basidiomycetous fungus Phlebia brevispora isolated from butt rot of Chamaecyparis obtusa (Japanese cypress) in 1997 in Nagasaki Prefecture, a sensitive polymerase chain reaction (PCR)-based assay was developed to specifically detect the fungus on-site. A species-specific primer for P. brevispora was derived from the internal transcribed spacer (ITS) region (containing 5.8S ribosomal DNA, ITS1 and ITS2) sequences of the fungus. The PCR assay was able to detect down to 1fg DNA (per 1µl PCR reaction mixture) and down to 0.2mg mycelium of P. brevispora (per 1g of decayed wood). The samples for on-site monitoring were collected in 2002 from the decayed tree stump in which P. brevispora had first been isolated. From the decayed tree tissue, P. brevispora could be detected by PCR assay even when its mycelium could not isolated from the tree tissue by culturing. This indicates that the PCR amplification using the specific primer developed here is a useful method for monitoring P. brevispora on-site.     

Preparation of anion-exchange resins from pine sulfuric acid lignin,one of the acid hydrolysis lignins

To utilize acid hydrolysis lignin effectively, chemical conversion to anion-exchange resin was investigated by two methods. Sulfuric acid lignin (SAL) was selected as a typical acid hydrolysis lignin in this experiment. Because it is less reactive, SAL was phenolated with sulfuric acid catalyst to yield reactive phenolized SAL (P-SAL) with p-hydroxyphenyl nuclei. One method was the restricted resinification of P-SAL followed by the Mannich reaction with formaldehyde and dimethylamine to yield a weakly basic anion-exchange resin with an ion-exchange capacity of 2.4mEq/g. Another method was to react resinified P-SAL with glycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with an ion-exchange capacity of 2.0mEq/g. The reaction of a simple P-SAL model compound with an epoxide suggested that the phenolic hydroxyl group of the p-hydroxyphenyl nucleus had slightly higher reactivity than that of the guaiacyl nucleus.Part of this report was presented at the 47th Lignin Symposium, Fukuoka, October 2002     

Concentration and molecular weight distribution of dissolved organic carbon in a mangrove creek in the Hinchinbrook area,Australia

The concentration and molecular weight distribution of dissolved organic carbon (DOC) are reported for a mangrove creek in the Hinchinbrook area, Australia. DOC concentration ranged from 1.0mg Cl–1 near the creek mouth to 2.2mg Cl–1 at the innermost part of the creek. There was no apparent spatial trend in molecular weight distribution of DOC, with a >300gmol–1 fraction accounting for about 70% of the total in all samples. DOC concentration fluctuated between 0.5 and 1.2mg Cl–1 over one tidal cycle. The samples collected at low tide and during the rising tide were dominated by DOC of >300gmol–1 and <300gmol–1, respectively. This suggested the export of high molecular weight DOC, probably originating from litter leachates, and the import of low molecular weight DOC to the creek.     

Reactivity of wood charcoal with ozone

We investigated the resistance of wood charcoal against ozone and estimated the half-life of the charcoal in air. The weight of wood charcoal prepared by the carbonization of Fagus crenata sawdust at 400°C (C-400) was not affected with up to 8.5% ozone while the charcoal prepared at 1000°C (C-1000) burned with 4.9% ozone. Pores with a diameter of approximately 100–200nm were observed on the surface of ozone-treated C-1000 by scanning electron microscopy, although no pores were found in ozone-treated C-400. The peak positions of the C1s spectra and the full width at half maximum of X-ray photoelectron spectrum peaks suggest that C-400 has an amorphous structure composed of aliphatic carbons and small aromatic molecules while C-1000 and activated charcoal (AC) are polyaromatic. It is likely that the aromatic layers of C-1000 and AC were destroyed and the edge carbon atoms were removed as CO or CO₂ by ozone oxidation. We estimated the half-life of C-1000 with ozone in air to be about 50000 years by assuming that the weight of C-1000 decayed exponentially. Thus, it is suggested that wood charcoal is stable on a geological time scale.     

Electromagnetic shielding efficiency of the electric field of charcoal from six wood species

Six wood species were carbonized under various carbonization temperatures and nonoxygen conditions to obtained charcoal. The effects of wood species, rate of temperature rise, and carbonization temperature on the electromagnetic shielding efficiency (ESE) of the electric field were investigated. The wood species used in this study were Japanese cedar, China fir, western hemlock, red oak, fortune paulownia, and Taiwan acacia. Tested materials were carbonized in a high-temperature oven under the following conditions: rate of temperature rise 1°–5°C/min; carbonization temperature 500°–1100°C, with temperature intervals of 100°C; maximum temperature maintained for 1h; and flow rate of nitrogen 300ml/min. The electromagnetic insulation strength system was used to detect the ESE of the electric field of charcoal. It was found that western hemlock and fortune paulownia charcoal showed maximum ESE values of of 36 and 61dB generated at a carbonization temperature of 1000°C. The charcoals derived from four other wood species showed maximum ESE values of 28dB for Japanese cedar, 23dB for China fir, 32dB for red oak, and 38dB for Taiwan acacia, respectively, at a carbonization temperature of 1100°C. The ESE value for fortune paulownia charcoal was similar to those of metal nets. The relations between ESE and logarithmic values of resistivity (log) could be represented by a negatively exponential formula.Part of this report was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

Preparation of liquid polyesterpolyols from glucose and its methyl derivative

Preparation of liquid polyols from d-(+)-glucose (Glc) and its derivative, methyl--d-glucoside (m-Glc), has been studied. Direct reaction of -caprolactone (CL) with Glc (CL:Glc = 2:1–5:1 in weight ratio) at 150°C using tin(II) 2-ethyl hexanoate (SnEht₂) (series A), in which melted Glc was suspended in CL, resulted in a dark-brown coloration of the reactants. The reaction was accompanied by formation of high molecular weight resins, a pH drop, production of water, and a considerable decrease in the hydroxyl value from the theoretically expected one. In the case of Glc/ethylene glycol (EG)/CL reaction system with SnEht₂ catalyst at 150°C (series B), in which the weight ratio of Glc to EG was fixed at 1:1, Glc dissolved in the EG/CL mixture, but the brown coloration of the reactant mixture still occurred. In this case, the formation of water was enhanced, but the other effects found in series A were suppressed to a considerable extent. In the m-Glc/CL/SnEht₂ reaction system (series C), in which m-Glc reacted with two to five times weight amounts of CL under the same conditions adopted in series A, development of the color, the production of high molecular weight materials and water, and the changes in pH and hydroxyl value were not observed. These results are discussed based on the chemical structural differences: Glc exists mostly in the hemiacetal form, but tautomerizes to the aldehyde, whereas m-Glc is an acetal and is protected from reversion to the aldehyde.     

Nitrogen use by <Emphasis Type="Italic">Pinus densiflora</Emphasis> trees growing on a Mt. Fuji lava flow

To quantify the nitrogen (N) use by Pinus densiflora trees growing on an infertile lava surface, N pools, N requirement and N uptake through fine roots and N deposition from the atmosphere were estimated. The N requirement and the N uptake of fine roots were 55.5kgNha^–1year^–1 and 39.7kgNha^–1, respectively. Thus, the ratio of N uptake to N requirement of the fine roots was 71.5%. Including fine-root contribution, the total N requirement of the P. densiflora trees was 98.6kgNha^–1year^–1, and the total N uptake was 64.2kgNha^–1year^–1. Thus, the N uptake of the P. densiflora trees was 64.1% of the N requirement, indicating that P. densiflora trees growing on an infertile lava surface obtain some of their N from below-ground organic material layers every year and the contribution of N storage in trees for their growth is not any higher than indicated in previous reports that excluded fine-roots contribution. The wet N deposition of our research forest was only 5.8% of the N requirement of the P. densiflora trees and only 8.9% of the N uptake. Movement of the below-ground organic material layer N concentrations in the F- and L-layers coincides with needle development and fine-root growth, suggesting the possibility that P. densiflora trees extract N from the organic N of those layers for growth.     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

Estimated stocks of organic carbon in mangrove roots and sediments in Hinchinbrook Channel,Australia

Aboveground and belowground root biomasses (Babove and Broot) were measured for young, isolated Rhizophorastylosa on Iriomote Island, Japan. The relationship between these two parameters was significant and given as the equation, Broot(g dry weight) = 0.394 × Babove(g dry weight) – 485 (r = 0.986). Multiple regression analyses also revealed good correlation between diameter and biomass of prop roots (Dprop and Bprop) and between prop root and root biomasses. Consequently, root biomass could be estimated from the measurements of diameter and biomass of prop roots using the multiple regression equation, Broot(g dry weight) = 80.0 ×Dprop(cm) + 0.86 ×Bprop (g dry weight) – 251. The relationship between DBH (diameter at breast height) and prop root biomass was also adequately described using an allometric equation.In Hinchinbrook Channel, Australia, redox potential (measured as Eh) and organic carbon stocks in the top 5cm of mangrove sediments were measured along a 600m transect from the frequently inundated, Rhizophora dominated zone on the creek edge, towards higher grounds, where Ceriops spp. became increasingly dominant. Eh values were about –60mV near the creek edge and increased to 260mV on higher grounds. Organic carbon stocks showed an opposite trend to Eh, with the values decreasing from about 360tCha–1 to 160tCha–1. At 18 sites, representing six different habitats, organic carbon stocks were also measured along with the DBH of mangrove trees. DBH was converted into aboveground biomass and then into root biomass using the equations obtained in the study on Iriomote Island. The average organic carbon stocks in the top 50 cm of sediments, aboveground biomass and root biomass were 296tCha–1, 123 tCha–1 and 52 tCha–1, respectively, and accounted for 64%, 25% and 11% of the total organic carbon stock.     

The occurrence of p-hydroxyphenylpropane units in the middle-lamella lignin of spruce (Picea abies)

Summary A sieving technique has been developed for the separation of middle-lamella fragments. The middle-lamella fraction as well as the whole wood and compression wood from Picea abies have been analysed by nitrobenzene oxidation and acidolysis in order to determine the content of p-hydroxyphenylpropane units in the middle-lamella lignin. These analyses revealed only traces of p-hydroxyphenylpropane units in the whole wood and in the middle-lamella fraction but considerable amounts were found in compression-wood lignin. This points to the fact that middle-lamella lignin is of guaiacyl nature and that earlier results reporting high proportions of p-hydroxyphenylpropane units in the middle lamella-lignin may be due to the inclusion of compression wood in the fraction studied. The acidolysis experiments further indicate that the middle-lamella lignin has fewer uncondensed -0-4 aryl ether structures than the whole wood lignin.The skilful technical assistance of Mrs. Britta Samuelsson and Mr. Johan Lindberg is highly appreciated. The author also thanks Dr. Knut Lundquist for supplying some of the reference compounds, and Dr. Hanne-Lise Hardell for help with the microscopic pictures     

Crystallinity of wood and the size of cellulose crystallites in Norway spruce (<Emphasis Type="Italic">Picea abies</Emphasis>)

X-ray diffraction was used to study variations in the crystallinity of wood and the average thickness and length of the crystallites of cellulose as a function of the number of the year ring in Norway spruce [Picea abies (L.) Karst.]. The crystallinity increased from ring 4 to ring 10 from the pith and was constant after ring 10. The crystallinity of mature wood was about 30% ± 5%. The average thickness and average length of the crystallites were 3.2 ± 0.1nm and 28 ± 2nm, respectively; and no systematic variation of these values with the number of the year ring was observed. The mean microfibril angle decreased near the pith but was constant in the mature wood.     

Water removal of wet veneer by roller pressing

High moisture content, flat sawn Japanese cedar (Cryptomeria japonica D. Don) veneer was compressed using a roller press to mechanically remove water. The amount of water removed depended on the amount of compression applied. At 60% compression, 400kg/m³ of water was removed. The process was not dependent on the size of the wood, the degree of compression, or the feed speed of the specimen. After compression, the remaining water contents were evenly distributed throughout the veneer regardless of the length of the specimen. The specimens did not completely recover to original thickness. High compression ratio and low temperature intensified the reduction of thickness. The bending strength after compression decreased in an inversely proportional manner with the thickness of the specimen and the compression degree.Part of this study was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

Gamma radiation sensitivity of larvae and adults of the red flour beetle, <Emphasis Type="Italic">Tribolium castaneum</Emphasis> Herbst

In this study, the susceptibility of larvae and adults of Tribolium castaneum (Herbst) to gamma radiation was investigated in the laboratory in Turkey. Gamma radiation was applied at 6 dose levels between 20 and 200Gy to 13–15day-old adults and at 5 dose levels between 20 and 180Gy to 18–20day-old larvae of T. castaneum. All experiments were performed in growth chambers maintained at 27±1°C and 70±5% r.h. The larvae proved to be the more susceptible stage, survival to the adult stage being prevented by exposure of the eggs to 100Gy; the adult stage was less susceptible. LD₅₀ and LD₉₉ values were determined as 19,75 and 42,97Gy for larvae and 33,21 and 64,50Gy for adult stage, respectively. It was concluded that 100Gy is the effective dose for both larval and adult stages.     

Changes in the physical and chemical properties of six Japanese softwoods caused by lengthy smoke-heating treatment

The effects of prolonged smoke-heating treatments on wood quality were investigated. Six Japanese softwoods were smoke-heated for 100 and 200h at a temperature of 75° ± 5°C, which was recorded inside the log. After smoke heating, wood quality, including moisture content, amounts of chemical components, relative degree of crystallinity (RDC) of cellulose, and sapwood color were examined. Moisture content decreased as a result of smoke heating, especially in sapwood, leading to a uniform distribution of moisture content within a log. Almost no difference was found in the amounts of chemical components between the control woods and the woods that were smoke-heated for 100h. However, in the wood that was smoke-heated for 200h, the amounts of holocellulose decreased, suggesting that thermal deterioration and/or degradation of hemicelluloses had occurred. We assume that the increase in RDC was caused by smoke heating with the crystallization of cellulose and/or thermal degradation of hemicelluloses. Almost no differences were found in sapwood color between the control woods and the woods that were smoke-heated for 100h. In the wood that was smoke-heated for 200h, however, L*decreased, whereas a* and b* increased. As a result, E*ab, showing the total color change, increased, resulting in a deeper color. These results suggest that thermal degradation of hemicelluloses was caused by smoke heating for over 100h. Therefore, smoke heating of softwood logs using a commercial-scale kiln should not exceed 100h.     

Physiological and psychological responses to prolonged light floor-impact sounds generated by a tapping machine in a wooden house

We investigated the physiological and psychological responses of nine normal men to the prolonged light floor-impact sounds of 60dBA and 80dBA generated by a tapping machine in a two-story wooden house. Blood pressure was measured, and a sensory evaluation was also conducted using the semantic differential method. The results obtained were as follows: (1) the increase in systolic blood pressure immediately after exposure to the light floor-impact sounds depended on the level of the sounds, (2) the variations in feelings due to the prolonged light floor-impact sounds were identified by factor analysis, and (3) the subjects showed no difference in comfortable feeling for the prolonged light floor-impact sounds of 60dBA and 80dBA, but differences in the variation of the systolic blood pressure were detected.Part of this research was presented at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997