Acceleration of the cure of phenolic resin adhesives VII: Influence of extractives of merbau wood on bonding

The influence of merbau wood extractives on the gelation rate of a phenolic adhesive and the effects of some cure accelerators on the bond performance of merbau plywood were investigated. The addition of merbau wood extractives slightly increased the gelation rate of the phenolic resin. This increase in the gelation rate was revealed to be due to a fall in the resin pH caused by addition of the extractives. The addition of cure accelerators, sodium carbonate and propylene carbonate, caused a considerable reduction in the hot-pressing time required for the merbau plywood to achieve sufficient bond qualities. Brushing veneer surfaces caused an increase in bond qualities. The combination of the cure acceleration and the surface brushing greatly improved the bondability of merbau wood. The main factor of gluing difficulty is considered to be the poor wettability of the veneer surfaces resulted from the accumulation of migrating extractives.Part of this work was presented at the 47th annual meeting of The Japan Wood Research Society, Kochi, April 3–5, 1997     

Condensation reactions of phenolic resins V: cure-acceleration effects of propylene carbonate

Propylene carbonate (PC) is known as one of the cure accelerators for alkaline phenol–formaldehyde resins. To elucidate the cure-acceleration mechanisms, the effects of PC on the condensation reactions of monomeric hydroxymethylphenols (HMPs) were investigated and compared with those of PC hydrolysate, sodium bicarbonate (NaHCO₃) and ethyl formate. Immediately after the reaction started, PC, decomposing itself simultaneously, accelerated the formation of the ortho-para methylene-bonded dimer of 2,4,6-trihydroxymethylphenol. This effect of PC was very similar to that of ethyl formate. To the contrary, PC hydrolysate accelerated the formation of the para-para methylene-bonded dimer throughout the course of the reaction. This effect of PC hydrolysate was identical to that of NaHCO₃. These results indicate that PC increases the reactivity of the ortho-hydroxymethyl group, presumably through transesterification. On the other hand, NaHCO₃ is formed by the hydrolysis of PC or decomposition of the transesterified HMPs and it increases the reactivity of the para-hydroxymethyl group.     

Condensation reactions of phenolic resins III: self-condensations of 2,4-dihydroxymethylphenol and 2,4,6-trihydroxymethylphenol (1)

This study reexamined the kinetics of the condensation reactions of hydroxymethylphenols with the purpose of elucidating the reaction mechanisms. This report discusses experimental results on the self-condensations of 2,4-dihydroxymethylphenols (2,4-DHMP) and 2,4,6-trihydroxymethylphenol (THMP), focusing on the order of reaction. The relations between the initial rates of reaction and the initial concentrations of reactants were investigated. Results quite different from those of previous reports were obtained. The order of reaction of the selfcondensation of 2,4-DHMP was found to be 1.1, which did not change with the alkali/2,4-DHMP molar ratio. The order of reaction of the self-condensation of THMP was found to vary with both the concentration of THMP and the alkali/THMP molar ratio. In the region of THMP concentrations above 1.5mol/l, the order of reaction was confirmed to be 2.0, which did not change with the alkali/THMP molar ratio. In the region of THMP concentrations below 1.0mol/l, the order of reaction varied with the alkali/THMP molar ratio, showing fractional numbers of 1.2–1.6. These results indicate that unimolecular reaction(s) and bimolecular reaction(s) take place simultaneously as the ratedetermining step in the condensation reactions of 2,4-DHMP and THMP and that the reaction mechanism changes with the species of reactant and, in some cases, with the reaction conditions.Part of this study was presented at the Wood Adhesives 2000 symposium, South Lake Tahoe, Nevada, USA, June 2000     

Condensation reactions of phenolic resins IV: self-condensation of 2,4-dihydroxymethylphenol and 2,4,6-trihydroxymethylphenol (2)

Kinetics of the self-condensation of 2,4-dihydroxymethylphenol (2,4-DHMP) and 2,4,6-trihydroxymethylphenol (THMP) were investigated to elucidate the mechanisms of the condensation of hydroxymethylphenols (HMPs). Rate equations were derived on the assumptions of the formation of quinone methide intermediates as unimolecular reactions and the occurrence of bimolecular reactions between undissociated HMPs, between undissociated HMP and dissociated HMP, and between dissociated HMPs. Rate constants were determined numerically by comparing the calculated reaction rates with observed ones. The results of analyses are as follows: (1) Both unimolecular and bimolecular reactions occur as the rate-determining steps during the self-condensation of 2,4-DHMP and THMP with low concentrations. (2) Nothing but bimolecular reactions occur as the rate-determining steps during the self-condensation of THMP with high concentrations. (3) Differences in the activation energy and the reaction rate due to the unimolecular process between 2,4-DHMP and THMP are small. (4) Rates of bimolecular reactions of THMP are about five times as large as those of 2,4-DHMP. (5) The values of the rate constants and the activation energy for the bimolecular reactions of THMP of low concentrations differ from those of THMP of high concentrations, indicating the difference in reaction mechanisms.     

Compressive deformation of wood impregnated with low molecular weight phenol formaldehyde (PF) resin III: effects of sodium chlorite treatment

To obtain high-strength phenol–formaldehyde (PF) resin-impregnated compressed wood at low pressing pressure, we investigated the effects of sodium chlorite (NaClO₂) treatment on wood prior to low molecular weight PF resin impregnation. Sawn veneers of Japanese cedar (Cryptomeria japonica) were treated with 2% aqueous NaClO₂ solution at 45°C for 12 h to remove lignin, and the process was repeated up to four times, resulting in weight loss of 21%. NaClO₂ treatment has shown considerable potential for high compression of PF resin-impregnated wood at low pressing pressure, especially after adding moisture to a content of 10%–11%. This deformation is further enhanced during pressure holding by creep deformation. The density, Young’s modulus, and bending strength of PF resin-impregnated veneer laminated composites that were treated with NaClO₂ four times and compressed at 1 MPa, reached 1.15 g/cm³, 27 GPa, and 280 MPa, respectively. The values in untreated PF resin-impregnated wood reached 0.8 g/cm³, 16 GPa, and 165 MPa, respectively.     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

A meta-analysis of the effects of nitrogen additions on base cations: Implications for plants, soils, and streams

The dominant base cations (BC; i.e., Ca²⁺, Mg²⁺, K⁺, and Na⁺) are important in buffering soil and water acidity in both terrestrial and aquatic ecosystems. Ca²⁺, Mg²⁺, and K⁺ are also important in many plant physiological functions. Because BC availability is affected by changes in the nitrogen (N) cycle, we conducted a meta-analysis of previously published data to determine if N fertilization alters the availability of BC in terrestrial and stream ecosystems across biomes. We include data from 107 independent studies published in 62 different articles, taking a holistic perspective on BC by examining their responses to added N in plant foliage, bulk soil, soil solution, and stream water. Our results suggest N fertilization may accelerate BC loss from terrestrial ecosystems over time periods less than five years. We found that N additions resulted in an overall 24% decrease in the availability of exchangeable Ca²⁺, Mg²⁺, and K⁺ in the bulk soil of boreal forest, temperate forest, and grassland biomes. Collectively, responses of BC in boreal forest, temperate forest, tropical forest, and grassland biomes increased following N fertilization by about 71% in soil solution and 48% in stream waters. Additionally, BC responses in foliage decreased in boreal forest and temperate forest biomes following N additions over time periods less than five years, but there were no significant changes over longer time periods. Despite large short-term shifts in BC responses following N additions, we did not find evidence of widespread negative impacts on ecosystems over time periods greater than five years. This analysis suggests effects of N addition on the availability of exchangeable BC may diminish over time. Although the effects on BC can be substantial over periods less than five years, there is little available evidence that N fertilization has had large-scale detrimental effects on the availability of BC needed for plant growth within terrestrial or aquatic ecosystems.     

Veneer strand flanged I-beam with MDF or particleboard as web material II: effect of resin type,application rate,strand dimension,and pressing time on the basic properties

Optimization of the manufacturing conditions of the veneer strand flanged I-beam invented in the previous study was investigated using different combinations of strand dimensions, resin types between web and flange, different pressing times, and different wood–resin moisture contents under conventional hot pressing conditions. The main results revealed that the strand dimensions have no effect on the bending properties of the flange part and the dimensional stability of the I-beam. Increasing the resin application rate between strands was found to improve the dimensional stability of the I-beams. The use of isocyanate (MDI) resin between web and flange significantly improved the bond strength between web and flange, the modulus of rupture of the I-beam, and the modulus of rupture of the flange part. Dimensional stability was also improved. Shortening the pressing time from 20 to 12min was found to be feasible. Using low wood-resin moisture content was found to interfere with the curing of the phenol–formaldehyde (PF) resin at the flange part resulting in poor quality beams. Of the three moisture content levels tested, 12% was found to be the optimal level for producing I-beams with balanced mechanical properties and dimensional stability.Part of this work was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, March 2003     

Modelling growth for two-storied stands: Incorporating an effect of shading on the tree growth into growth and yield models

The objective of this paper is to review research into growth and yield modelling for two-storied plantation forests. Difficulty with modelling growth for this kind of forest, compared with pure even-aged forests, is mentioned. Then research in this field is divided into three parts and described. First, growth models and equations which were driven theoretically from biological assumptions and may be available to develop growth models for two-storied stands are reviewed. Secondly, research into methods of controling light levels and the relationship between the growth of trees and light level beneath a canopy are reviewed. Thirdly, growth models developed for two-storied stands, especially two-storied plantation forests, are reviewed. In conclusion, some problems which are still left in this field are pointed out.     

A trial to detect optimal pin-pricking timing in evaluating the ability to form traumatic resin canals of <Emphasis Type="Italic">Cryptomeria japonica</Emphasis> for selecting resistant trees to <Emphasis Type="Italic">Semanotus japonicus</Emphasis> (Coleoptera: Cerambycidae)

A trial to detect optimal pin-pricking timing in evaluating the ability to form traumatic resin canals (TRCs) of Cryptomeria japonica was examined to select resistant trees to Semanotus japonicus using 14 clones in 2001 and 2002. Resistance to S. japonicus and the ability to form TRCs in the phloem was evaluated by inoculating newly hatched larvae in the bark and by a pin prick, which was conducted every 10 days (four times) on the trunk around the larval phloem-feeding period, respectively. The larval survivorship varied greatly among clones for both years. The mean appearance of newly formed TRCs was generally higher in late treatment for both years, and the tangential width of them was also higher in 2001, whereas those of pre-formed TRCs were not higher for either year. The larval survivorship did not show significant correlations with the appearance and the width of pre-formed TRCs on all treatments. However, it showed significant negative correlations with the appearance of newly formed TRCs on the second and third treatments on the 2-year-old layer, although this was not significant with the width of them. This suggests that resistant clones might have the mechanism of rapidly forming TRCs when just at the stage of newly hatched larval entering the phloem. Thus, although the relationship between the appearance and the width of newly formed TRCs is not clear, pin-pricking treatment when the newly hatched larvae just enter the bark may be one of optimal times for the evaluation of the resistance of C. japonica to S. japonicus. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.