Condensation of lignin during heating of wood

Summary The structural change of lignin during heating of wood was investigated quantitatively by a method combining nucleus exchange and nitrobenzene oxidation. Lignin modification during heating was mainly a diphenylmethane type condensation. About 40 and 75% of noncondensed units in protolignins were converted to diphenylmethane type units by heating of dry and wet wood meals up to 220 °C, respectively. On the other hand, during heating of modified lignin (dioxane lignin) various types of modifications in addition to diphenylmethane type condensation occurred. Lignin modification via the diphenylmethane type condensation was proposed as a new route for its utilization.     

Activities of some enzymes of lignin formation in reaction wood of Thuja orientalis and Metasequoia glyptostroboides 2

Summary To elucidate biochemical features leading to p-hydroxyphenyl-rich lignin in gymnosperm reaction wood the activities of the following five enzymes involved in the biosynthesis of p-hydroxyphenyl lignin were compared in reaction and opposite woods: phenylalanine ammonialyase (EC 4.3.1.5), cinnamate 4-hydroxylase (EC 1.14.13.11), p-hydroxycinnamate: CoA ligase (EC 6.2.1.12), cinnamyl alcohol dehydrogenase (EC 1.1.1.-) and peroxidase (EC 1.11.1.7). The enzyme activities in the reaction woods of Thuja orientalis and Metasequoia glyptostroboides were remarkably higher than those in the opposite woods, reflecting the higher contents of p-hydroxyphenyl lignin in reaction wood.This work was partly supported by the Grant-in-Aid for Scientific Research (548047) from the Ministry of Education, Science and Culture of Japan. We thank the Ministry of Education for the support     

Distribution of lignin in normal and tension wood

Summary The distribution of lignin in normal and tension wood of four hardwood species has been studied by examination in the electron microscope of the lignin skeletons remaining after removal of the polysaccharides with hydrofluoric acid. In normal wood fibers, the S₁ had a higher lignin concentration than the S₂ layer, which was not as highly lignified as in conifer tracheids. Vessels had a high concentration of lignin in both normal and tension wood, while the extent of lignification of the parenchyma was variable.In tension wood fibers, the S₁ and S₂ layers were highly lignified. A thick, unlignified G-layer was often associated with an extremely thin S₂ layer with a high concentration of lignin. In both normal and tension wood, the lignin had the same orientation as the cellulose micro-fibrils in the different cell wall layers. The results confirm the earlier conclusion that, in the species investigated, the same amount of lignin is present in gelatinous as in normal fibers. Evidently, the lignification mechanism operates normally in the non-gelatinous layers of the fibers, as well as in the vessels and in the parenchyma of tension wood.

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Zusammenfassung Die Ligninverteilung im Normalholz und im Druckholz von vier Laubhölzern wurde untersucht. Die Ligningerüste, die nach der Entfernung der Polysaccharide durch Fluorwasser-stoffsäure übrigblieben, wurden im Elektronenmikroskop beobachtet. In den Normalholzfasern hatte die S₁-eine höhere Ligninkonzentration als die S₂-Schicht, die weniger lignifiziert war als in den Koniferentracheiden. Die Gefäße hatten eine hohe Ligninkonzentration in sowohl Normal-als in Zugholz, während der Lignifizierungsgrad der Parenchymzellen variierte.In den Zugholzfasern waren die S₁- und S₂-Schichten völlig lignifiziert. Eine dicke, unlignifizierte G-Schicht war oft mit einer außerordentlich dünnen S₂-Schicht, die eine hohe Ligninkonzentration zeigte, verbunden. Sowohl im Normal- wie auch im Zugholz besaß das Lignin dieselbe Orientierung wie die Cellulosemikrofibrillen in den verschiedenen Zellwandschichten. Die Ergebnisse bestätigen den früheren Schluß, daß in den hier untersuchten Laubhölzern in den gelatinösen und in den normalen Fasern dieselbe Ligninmenge vorliegt. Offenbar läuft der Mechanismus der Lignifizierung in den S₁- und S₂-Schichten der gelatinösen Fasern des Zugholzes normal ab.

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This investigation was supported by the United States Department of Agriculture, Forest Service, through Forest Service Research Grant No. 1, which is hereby gratefully acknowledged.     

Effect of tool angles on the chips generated during milling of wood by straight router-bits

 The effect of tool angles on the shapes of chips generated by parallel-to-grain and end-grain milling was explored for China fir and maple under fixed spindle and feed speeds and cutting depth. The milling path was up-milling by straight router-bits with a diameter of 12 mm. The chip shapes could be distinguished as five types: spiral, splinter, flow, thin, and granules or powder. The flow and thin chips were generated most often (on a weight percentage basis) for all tool angles investigated for parallel-to-grain and end-grain milling of China fir and maple. More granule chips were produced with parallel-to-grain milling than with end-grain milling for both woods. The measured chip thickness (t′) was thicker than the calculated thickness (t _max). Thicker and longer maple chips were produced by end-grain milling than by parallel-to-grain milling. The tool geometries of 40°/15° (sharpness of the angle–rake angle), 50°/15°, and 60°/15° for China fir and 40°/25°, 50°/5°, and 60°/5° for maple produced relatively more flow chips with parallel-to-grain milling. Furthermore, the tool geometries of 40°/5°, 50°/15° and 60°/25° produced more flow chips (weight percentage) by end-grain milling of China fir and maple. Received: May 23, 2001 / Accepted: June 28, 2002 Acknowledgment This study was supported by a grant from the National Council of Science, Taiwan (NSC89-2313-B-415-011).     

Interaction of lignin and polysaccharides in beech wood (Fagus sylvatica) during drying processes

Summary ¹³C CP MAS NMR spectroscopy was used to characterize the structural changes of cell wall polymers in beech wood Fagus sylvatica during drying processes. The analysis of five wood samples, namely, untreated, untreated dried, pre-treated by steam and/or NaOH subjected to drying showed partial depolymerization of lignin component as well as the change of the ratio of the crystalline and of the amorphous parts of cellulose as the consequence of wood pre-treatment. In addition, T_1ρ(¹H) relaxation times were determined in beech wood sample pre-treated with steam at 135 °C and the lignin isolated from this sample. The magnitudes of the relaxation times were found comparable in both samples as well as in the lignin-cellulose model compound. These unique T_1ρ (¹H) values indicate that spin diffusion is complete and homogeneous due to spatial proximity of spins and confirmed the formation of lignin-cellulose complex during thermal treatment of wood. Received 30 June 1997     

Notes on the spectrophotometric determination of lignin in wood samples

A method developed by Johnson et al. whereby lignin is determined spectrophotometrically was found to yield lignin values which showed variations of up to 10%. The presence of water in, and the freshness of the digestive mixture together with the grade of acetic acid used and the time between dilution and measurement of absorbance were found to affect the reproducibility of the method.     

Enzymic isolation of lignin from wood and pulps

After enzymic hydrolysis of polysaccharides in milled wood or pulp the unhydrolysed lignin residue becomes soluble in certain polar solvents. Extensive disintegration of the wood is necessary to obtain a sufficient accessibility toward the enzyme. For milling a porcelain rotary ball mill is recommended. A relationship has been found between the milling energy, which is proportional to the size of the mill, the milling time, and the yield of ball-milled wood lignin (BMWL). Enzymatically isolated lignin (EIL) requires a critical milling time which is shorter than that for obtaining maximum yields of BMWL. A procedure for isolation of the total lignin content from wood and pulps in the form of three fractions has been developed, giving a water soluble, low molecular carbohydrate-lignin complex by water extraction of ball-milled wood, a BMWL-carbohydrate complex by subsequent extraction with dioxane, and a EIL-carbohydrate complex by dioxane extraction of the residue after enzymic hydrolysis.     

木片散堆碎料水分迁移系数的研究

本文首次提出利用梯度转换法,实验测定动态传质控制方程中的质扩散系数及传质边界条件中的质交换系数,求算了表面以下蒸发界面深度及其对蒸发速率与相对蒸发深度的关系。实验表明,多孔物料表面下的相对蒸发深度在1%以下时,对质迁移率的影响极为显著。质交换系数也是蒸发界面深度的函数。质扩散系数是含水率的函数。本文采用变系数分段线性化的方法,利用质扩散方程的解析解验算了所求出的质扩散系数、质交换系数及蒸发界面深度的可靠性。理论验算表明,无量纲质迁移势的理论值与实验值之间的相对误差不大于6%,从而说明,利用梯度转换法测定木片料床的质迁移系数的方法是可行的。     

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     

Studies on opposite wood in conifers part III: Distribution of lignin

Summary The distribution of lignin in opposite wood has been studied by removing the polysaccharides with hydrofluoric acid and examining the resulting lignin skeletons in the electron microscope. The thick S₃ layer was more highly lignified than the S₁ and S₂ layers in Abies balsamea, Picea rubens, Pinus resinosa, and Tsuga canadensis. In Picea rubens, but not in the other species, there was, adjacent to the S₃ layer, a transition zone in S₂ with a high concentration of lignin. The S₃ layer varied considerably in thickness and was often buckled, especially in the latewood. The structure of the bordered pits was that observed in the original wood. The margo, the torus, and the initial pit border were all highly lignified.This paper is dedicated to Dean Edwin C. Jahn in honor of his 70th birthday.     

Dynamic simulation of disintegration of wood chips caused by impact and collisions during the steam explosion pretreatment

Steam explosion (SE) pretreatment produces damaged and disintegrated biomass with a large surface area which facilitates enzymatic hydrolysis for the production of biofuels and other value-added chemicals. It was observed during experiments that wood chips disintegrate into smaller pieces because of collisions and impact with each other and the walls of the SE equipment. In this study, these events were simulated using the finite element method. Wood chips were simulated in this model as a linear elastic material until failure. The damage initiation was identified using Hashin’s damage initiation criteria. Once the damage was initiated, additional loading caused the evolution of damage, i.e. degradation and breakage of the material, which was modelled using the material property degradation model and deletion of the failed elements. Elastic and strength properties of spruce wood were estimated at ambient conditions (12 % moisture content at 20 °C) and at SE conditions (30 % moisture content at 160 °C). Comparison of simulations performed using material properties at ambient and SE conditions revealed that the damage in wood chips significantly increased because of the steam treatment. The effects of wood chip velocity and orientation at the time of impact were studied as well. It was found that wood chips moving at high velocity and impacting with the steel wall in the radial direction acquire the most damage.     

Studies on milled wood lignin from spruce Part II. Electron microscopic observations on the milled wood

Summary Wood samples that had been ball-milled and extracted with dioxane under various conditions were observed in the scanning electron microscope. Ball milling causes not only a reduction in size of the cells and cell walls but also an internal disruption of the particles. The intensity of milling has a larger influence on the particle size than a prolongation of the milling time. A direct relation was established between particle size and the previously determined yield of purified milled wood lignin.Submitted by Erwin-Riesch-Stiftung zur Förderung der wissenschaftlichen Forschung.     

Degradation of wood surfaces during natural weathering. Effects on lignin and cellulose and on the adhesion of acrylic latex primers

Summary Radiata pine veneers and blocks were exposed to natural weathering under Australian summer conditions over a period of 30 days. Infrared spectroscopy revealed that there was perceptible surface delignification after 4 hours exposure, substantial surface delignification after 3 days exposure and almost complete surface delignification after 6 days. Rapid lignin degradation was also suggested by measurements of the acid insoluble lignin content of weathered veneers. Viscometry determinations on holocellulose samples from weathered veneers and unweathered controls indicated significant depolymerisation of cellulose after 4 days exposure. A tape test was used to assess the adhesion of acrylic latex primers to weathered blocks. The adhesion of exterior acrylic primers decreased on weathered wood surfaces and was significantly lower on specimens that were weathered for 5 to 10 days. An oil-modified acrylic primer showed greater adhesion to weathered wood surfaces. Primer adhesion was lower on weathered radial surfaces than on similarly exposed tangential surfaces. The practical implications of these findings for the coating of exterior wood with acrylic latex primers are discussed briefly.The authors wish to thank Dr. A. J. Michell for FTIR spectral determinations and the Australian Research Council small grants scheme for financially supporting part of the work     

Chemical structural elucidation of total lignins in woods I: fractionation of the lignin in residual wood meal after extraction of milled wood lignin

Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

Drying and anatomical characteristics of sugi wood attacked by bacteria during pond storage

Seven species of bacteria were isolated and identified from ponded sugi (Cryptomeria japonica D. Don) logs, and six species showed potent wood-degrading activities. To evaluate the effects of these isolated bacteria on the drying and anatomical characteristics of wood, small fresh blocks of sugi were immersed in water suspensions containing bacteria for 1–7 months. The permeability and drying properties were evidently improved. Most of the encrusting substances adhering to the cell lumens and the pit chambers were removed, and the pit membranes were destroyed. These anatomical changes due to bacterial activity were assumed to improve the permeability of sugi wood.Part of this report was presented at the 40^th annual meeting of the Japan Wood Research Society, Tsukuba, April 1990; the 41^st annual meeting of the Japan Wood Research Society, Matsue, April 1991; and the IUFRO XX World Congress, Tampere, August 1995     

Effects of temperature,relative humidity and time on survival of pinewood nematodes in wood chips

The survival of two Canadian isolates of the pinewood nematode, Bursaphelenchus xylophilus, in coniferous wood chips under different temperatures, relative humidities and time intervals was investigated in vitro. The nature of the survival mechanism was examined and it was shown that the nematode's prolonged survival in the chips depended on its dispersal third larval stage. The possibility of PWN-infested wood chips spreading PWN-induced pine-wilt disease to forests is discussed.     

The effect of lignin on the bending properties and fixation by cooling of wood

To clarify the effects of lignin on the fixation of bending deformation by cooling, cooling set for delignified woods with various lignin residues were investigated to compare with mechanical and dynamic viscoelastic properties. Bending tests showed that steep reductions occurred in the modulus of elasticity and modulus of rupture with delignification during the initial stage of delignification. The dynamic viscoelastic measurements revealed that the peak temperature of tan δ due to micro-Brownian motion of lignin was reduced with delignification, and the peak disappeared in the temperature range of 5°–100°C for the specimens that had lost more than 21% of their weight. On the other hand, no clear change in residual set was found in the range of 0%–15% of weight loss in spite of a marked reduction in lignin content. Subsequently, set decreased steeply for the specimens delignified beyond 15% of weight loss. It was suggested that cooling set is not determined solely by lignin content but is influenced by changes in the quality of lignin due to delignification. Lignin quality affects the balance of the elastic potential to recover from deformation and its viscosity, which is an indication of resistance against flow. Part of this report was presented at the 57th Annual Meeting of the Japan Wood Research Society, Hiroshima, August 2007     

Distribution of lignin in normal and compression wood of Pinus taeda L.

Summary The distribution of lignin in normal and compression wood of loblolly pine (Pinus taeda L.) has been studied by the technique of lignin skeletonizing. Hydrolysis of the wood carbohydrates with hydrofluoric acid left normal wood tracheids with a uniform distribution of lignin in the S1 and S2 cell wall layers. However, the S3 region of both earlywood and latewood tracheids consistently retained a dense network of unhydrolyzable material throughout, perhaps lignin.Lignin content in compression wood averaged about 7% more than in normal wood and appears to be concentrated in the outer zone of the S2 layer. The inner S2 region, despite helical checking, is also heavily lignified. The S1 layer, although thicker than normal in compression wood tracheids, contains relatively little lignin.Ray cells, at least in normal wood, appear to be lignified to the same extent, if not more so in certain cases, than the longitudinal tracheids. Other locations where lignin may be concentrated include initial pit border regions and the membranes of bordered pits.This report is a detailed excerpt from the Ph. D. dissertation of R. A. P. Financial support provided by the College of Forestry at Syracuse University and the National Defense Education Act is hereby gratefully acknowledged.     

Quantifying lignin and holocellulose content in coniferous decayed wood using near-infrared reflectance spectroscopy

To determine the independent decomposition rates of lignin and cellulose of decayed woody debris, a technique for the rapid analysis of lignin and cellulose is required. We applied a near-infrared spectroscopy (NIRS) technique to measure the lignin and holocellulose content in decayed wood. We succeeded in creating partial least-squares (PLS) models to estimate the lignin and holocellulose content in the decayed wood of five species using NIR spectra. Although the accuracy was acceptable for the estimation of a five-species mixed model (R ² = 0.970 for lignin and R ² = 0.962 for holocellulose), it was further improved when the model was applied to each species independently. This combination of NIRS and a PLS model is a valuable tool for the determination of the lignin and holocellulose content in decayed wood. The technique is time efficient (3 min per sample) and non-hazardous (no acid treatment is required).