Lignin as a cross-linker of acrylic acid-grafted carboxymethyl lignocellulose

Cunninghamia lanceolata wood meal samples with different lignin contents after delignification with an acidic NaClO₂ system were carboxymethylated, and the degree of substitution (DS) and the distribution of the carboxymethyl (CM) groups were investigated by proton nuclear magnetic resonance (¹H NMR) spectroscopy. Cellulose samples prepared from bleached kraft softwood pulp, food-grade konjac mannan, and commercial oat xylan (containing 10% arabinosyl and 15% glucosyl residues) were also investigated. The chemical shift of methylene protons in ¹H NMR spectra of CM groups of carboxymethyl konjac mannan and commercial oat xylan appeared in the same region as those of carboxymethylcellulose. The DS of carboxymethyl lignocellulose (CMLC) increased slightly from 1.36 to 1.48 with decreasing lignin content, but the water solubility of CMLC clearly increased with decreasing lignin content. It was suggested that the covalent linkages between lignin and cell-wall polysaccharides play the role of cross-linker in CMLC. Water absorbents were synthesized by graft-copolymerization of acrylic acid onto CMLC samples with different lignin contents. The highest level of water absorbency was obtained from CMLC containing 14% of lignin, suggesting the importance of lignin as the cross-linker.     

The use of near-infrared scanning for the prediction of pulp yield and chemical properties of Pinus patula in the Mpumalanga escarpment area of South Africa

Near-infrared (NIR) scanning technology is regarded as a potential tool for rapid determination of wood properties, which can substitute time-consuming and costly traditional methods. Pinus patula is the most important softwood species in South Africa, and this study is aimed at developing NIR calibration models for quick prediction of its pulp yield and chemical composition. A total of 85 trees from 17 plots, covering the range of site conditions in the Mpumalanga escarpment area, were sampled. Two samples were taken from each tree: a 1 m billet above breast height and a 20 mm disc at breast height. The billet was pulped using the kraft pulping process to determine pulp yield. The disc was ground into sawdust and the chemical composition was determined using conventional wet chemistry. Sawdust was scanned on a NIR spectrophotometer to produce NIR spectra. Calibration models to predict pulp yield, cellulose and lignin content were developed by applying chemometrics and partial least squares regression. Validation and determination of prediction accuracy of the models were performed using independent data. The prediction of cellulose and lignin were acceptable with correlations of determinations (r ²) of 0.71 and 0.70 respectively. Standard errors of prediction were generally low (less that 0.86) for all the models. The prediction r ² for both total and screened pulp yield were only 0.62. Although the cellulose and lignin models can be used with confidence, the expansion of the sample size for follow-up research must be considered in order to increase the variability of tested wood properties and improve the prediction strength of the models. The NIR calibration provided in this study can contribute to the efficient examination of forest site-to-wood quality relationships that would enhance precision forest management and wood processing efficiency.     

Changes of major chemical components in larch wood through combined treatment of drying and heat treatment using superheated steam

The effects of the combined treatment of drying and heat treatment using superheated steam (SHS) were studied relative to the changes of the major chemical components in larch wood. The green lumber was dried and heat-treated in SHS conditions of 250 °C and 0.5 MPa for 18 h, and the relative percentage contents of sugars, lignin, and extractives were investigated and compared with the relative percentage contents in the lumber heat-treated in hot air conditions of 250 °C and atmospheric pressure for 18 h. After both heat treatment methods, the relative percentage contents of xylan, mannan, galactan, and arabinan were greatly decreased, whereas that of the Klason lignin was increased, additionally that of glucan and extractives remained almost unchanged. Lignin may bind with furan compounds decomposed from hemicellulose following heat treatment, thus contributing to the increase in the apparent relative percentage contents of the Klason lignin. In addition, the condensate collected in the condenser after combined drying and heat treatment using SHS was investigated qualitatively and quantitatively by high-performance liquid chromatography (HPLC). A large amount of furfural and acetic acid decomposed from hemicellulose was detected and some sugar components composed of cellulose and hemicellulose were detected in the liquid condensate.     

Rapid assessment of coniferous biomass lignin–carbohydrates with near-infrared spectroscopy

The main objective of this research was to construct accurate near-infrared reflectance (NIR) models of wood chemistry. Wet chemistry procedures and high-performance liquid chromatography methods were employed to analyze the chemical composition of southern pine. The NIR spectra were collected from 21 wood samples, which were milled down to different particle size classes. NIR calibration and prediction models were established using two modeling methods with different pretreatments. Furthermore, the spectrum range used in the NIR models was refined to achieve higher prediction accuracy. Results showed that NIR model precision could be improved considerably by decreasing the particle size to a very fine powder coupled with a targeted spectrum range. Superior prediction models for lignin and holocellulose content were constructed, while models for extractives and cellulose contents were also strong.     

Non-isothermal autohydrolysis of Eucalyptus wood

Non-isothermal autohydrolysis treatments of Eucalyptus globulus wood were carried out in batch reactors in order to assess the kinetics of hemicellulose degradation, as well as the effects caused on cellulose and lignin. Experiments were carried out at a liquor to wood ratio of 8 g/g, and two heating profiles were explored. The maximum temperature considered was 224 °C, and the longest reaction time was 0.94 h. The experimental variables considered were solid residue yield, solid residue composition and composition of liquors. Up to 90.4% of the initial xylan was removed in treatments, which also caused some delignification (up to 13.8% of the initial lignin was removed), whereas cellulose was almost quantitatively retained in solid phase. The conversion of xylan into xylooligomers, with further hydrolysis to xylose and decomposition of this sugar into furfural was assessed by means of a kinetic model based on sequential, first order reactions involving kinetic coefficients with Arrhenius-type dependence on temperature. Received 23 November 1999     

Comparison of <Emphasis Type="Italic">Pinus taeda</Emphasis> L. whole-tree wood property calibrations using diffuse reflectance near infrared spectra obtained using a variety of sampling options

A necessary objective for tree-breeding programs, with a focus on wood quality, is the measurement of wood properties on a whole-tree basis, however, the time and cost involved limits the numbers of trees sampled. Near infrared (NIR) spectroscopy provides an alternative and recently, it has been demonstrated that calibrations based on milled increment cores and whole-tree data can provide good estimates of whole-tree properties. Several options exist for sampling standing trees and the aim of this study was to compare wood property calibrations based on NIR spectra collected from samples obtained using different sampling methods. Calibrations for whole-tree lignin and basic specific gravity based on NIR spectra from whole-tree chips (milled or intact) had the strongest statistics, calibrations based on NIR spectra from milled increment cores were similar. Other options for sampling the tree (drill shavings, etc.) gave errors that were too large for practical applications. If an increment core is going to be used to estimate whole-tree properties, it is recommended that it be dried and milled prior to analysis.     

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).     

Kernel regression methods for the prediction of wood properties of Pinus taeda using near infrared spectroscopy

Near infrared diffuse reflectance spectra collected in 10-mm sections were used for the estimation of air-dry density (AD), microfibril angle (MFA), stiffness (MOE), tracheid coarseness (COARS), and tracheid wall thickness (WTHICK) in wood radial strip samples obtained at breast height (1.4 m) from 60 Pinus taeda trees. Calibration models were developed using traditional partial least squares (PLS) and kernel regression. The kernel methods included radial basis functions-partial least squares (RBF-PLS) and least-squares support vector machines (LS-SVM). RBF-PLS and LS-SVM models outperformed PLS-CV calibrations in terms of fit statistics. MFA and MOE, two properties that exhibited nonlinearity, showed the most significant improvements compared to PLS. In terms of predictive ability RBF-PLS performed better than PLS for the prediction of MFA, MOE, and COARS. LS-SVM showed better prediction statistics in all cases, except for WTHICK that gave similar statistics compared to PLS and was superior to RBF-PLS. By adding statistically significant factors to the PLS regressions, it was possible to capture some of the nonlinear features of the data and improve the predictive ability of the PLS models.     

Differential calometric analysis of wood and wood components

Summary The prolysis of cellulose, hemicelluloses, lignin preparations, and wood was studied by differential calorimetric analysis (DCA) for the range of 25° to 800° C. The test samples included powdered and filter paper celluloses; hardwood xylan; softwood galactoglucomannans, compression wood galactan, and arabinogalactan; a synthetic (DHP), sulfuric acid, Björkman, Brownell, and cellulase lignins; and unextracted and extracted hardwoods and softwoods. Heats of reaction were determined from the DCA thermal transition areas. Distinct differences were found between the thermograms of each hemicellulose and lignin sample. Although wood species could not be separated thermally, hardwood and softwood thermograms differed because of the hemicellulose degradation pattern.Trade names and company names are included for the benefit of the reader and do not imply any endorsement or preferential treatment of the product by the U.S. Department of Agriculture.Formerly Research Technologist, Forest Products Laboratory, Forest Service, U.S. Department of Agriculture. The Laboratory is maintained at Madison, Wis. 53705, in cooperation with the University of Wisconsin. Present address: The Pennsylvania State University, University Park, Pennsylvania 16802.     

Chemical characterization of wood and extractives of fast-growing Schizolobium parahyba and Pinus taeda

This study aims to evaluate the chemical composition of wood and extractives of Pinus taeda and Schizolobium parahyba (guapuruvu) as potential feedstock for new applications in the biorefinery industry. For this purpose, their content of α-cellulose, hemicellulose, insoluble lignin, hot water solubility, NaOH_1% solubility, inorganic materials (ash), and monomeric sugars by high-performance liquid chromatography was quantified. Attenuated total reflectance infrared spectroscopy and thermogravimetric analysis were also used to complete the physicochemical characterization of the studied woods. The extractives were obtained by soxhlet extraction with ethanol:toluene and dichloromethane and identified with pyrolysis-gas chromatography/mass spectroscopy technique. The results showed that guapuruvu wood has the higher amount of hemicellulose (16%) when compared to pine wood (10%), which resulted in higher solubility in alkali solution. Furthermore, in relation to other biomasses, the two woods presented more percentage of lignin and minor content of hemicelluloses. The P. taeda wood presented the highest percentage of extractives mainly composed of fatty acids and aromatic hydrocarbons, while guapuruvu wood had a higher percentage of phenolic compounds and also fatty acids. Both the materials have low content of extractives with dichloromethane and were mainly composed of lipophilic compounds.     

古建木构件化学组分近红外光谱分析

在材种鉴定的基础上,通过近红外光谱(NIRS)定性分析了建成约600 a的木造古建筑木构件的化学组分,结合木构件化学组分定量分析,与现代木材相比较,探讨了近红外光谱技术评价木构件老化的可行性。结果表明:近红外二阶导数特征性谱带反映了木材纤维素以及半纤维素和木质素的基团信息,而其差谱反映出木构件与对照样化学组分变化。这些光谱特征与传统的化学组分定量分析的结果非常一致:纤维素和半纤维素相对含量减少而木质素相对含量增加,与各种组分谱带差谱的增减相对应。此外,在5 882,5 587和5 464 cm-1等谱带处反映的纤维素结晶和半结晶区的光谱信息,差谱观察到木构件与现代材落叶松之间化学组分的不变或减少,其结果与X射线衍射(XRD)方法获得的木材结晶度分析结果相一致。通过NIRS定性分析木构件化学组分及结晶度变化,接近于现场检测方法,使用便携式NIRS,在古建筑木构件端头裸露部位获取光谱信息,能够实现现场对木材化学组分的无损定性评价。本实验结果也表明,除了常规的红外光谱(FT-IR)、XRD分析技术,NIRS技术对于木构件老化状况的评价是一种有潜力的无损检测方法。     

徐州出土汉代棺木用材树种鉴定及其化学性质

木材是人类日常生活的常见材料,也是从古至今人类文明与民族文化的重要载体。伴随着考古发掘工作的进行,来自不同地区、不同朝代的大量木质文物出土并需要持续保护,因此掌握出土木质文物所用的木材树种情况,并研究其化学组分的降解状态,可为制定合理的木质文物修复和保护方案提供科学依据。通过对徐州万达汉墓墓群中1号与4号墓出土棺木进行取样和对标准三切面的切片进行观察,根据三切面显微构造特征对棺木所用木材树种进行鉴定,经与标准切片比对,结果表明M1c、M1oc、M4c、M4oc棺木树种分别为楠木(Phoebe sp.)、硬木松(Pinus sp.)、梓木(Catalpa sp.)、榉木(Zelkova sp.)。进一步采用荧光显微镜与傅里叶变换红外光谱、X射线衍射相结合的方法,分析棺木的主要化学组分降解情况。结果表明:与现代健康材相比,古木在长期埋藏过程中,木材的主要多糖类化学组分纤维素和半纤维素降解严重,纤维素结晶度降低;古木各类型细胞中木质素的自发荧光效应均减弱,且红外光谱分析表明木质素化学结构发生改变;古木在埋藏过程中木材的整体构造保存较好,但主要化学组分发生了降解,这与其地下饱水低氧的埋藏环境有很大关系。     

Determination of fiber length and juvenile and mature wood zones in Acer velutinum Boiss. trees grown in Iran

In our investigation we studied fiber lengths and the transition age from juvenile to mature wood in Acer velutinum Boiss. For this purpose, samples from three normal maple trees at a Noshahr site in northern Iran were selected. Disks were cut at breast height. Test samples were taken along a radial direction from the pith to the bark, accounting for every ring during a 48-year period. We used the Franklin method to distinguish between fibers of juvenile and mature wood. The results show that the fiber length increased along the radial direction from the pith to the bark. The transition age between juvenile and mature wood was determined at the 14th annual ring from the pith.     

Growth and wood density of Pinus taeda L. as affected by shelterwood harvest in a two-aged stand in Southern Brazil

Pine plantations are an important wood source in Brazil, with Pinus taeda being most frequently planted. Most pinewood is directed to the paper and pulp industry, but there is an increasing demand for wood for solid end-uses, requiring large stems from longer rotations which can be obtained using P. taeda as the canopy in two-aged stands. We evaluated radial growth and wood density at different stem heights of P. taeda in the highlands of Southern Brazil over a production period of 36 years and subjected to shelterwood harvest. Cross-sectional disks were obtained from 15 trees in different stem heights; 10 were used for growth analyses and 5 for growth and density analyses. We used disk images and X-ray techniques for growth and density analyses, respectively. Samples were analyzed for ring (width and density), earlywood, and latewood (width, density, and proportion). Ring width varied between 0.4 and 1.7 cm, with the widest rings in the first years (3–5 years.) of growth. Ring density increased with age, with higher densities on the lower stem portions. Mature wood started to be formed from the 16th ring onwards. Shelterwood harvest affected both ring width and density, but the effects on ring width lasted for at least 5 years, while the effects on wood density were short-lasting. Mature P. taeda trees increased their size after the shelterwood harvest without compromising their wood density. Longer production periods of P. taeda as retained trees in the canopy of two-aged stands provide high-quality wood for structural purposes.

     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Determination of lignin and extractive content of Turkish Pine (<Emphasis Type="Italic">Pinus brutia</Emphasis> Ten.) trees using near infrared spectroscopy and multivariate calibration

Determination of quality parameters such as lignin and extractive content of wood samples by wet chemistry analyses takes a long time. Near-infrared (NIR) spectroscopy coupled with multivariate calibration offers a fast and nondestructive alternative to obtain reliable results. However, due to the complexity of the NIR spectra, some wavelength selection is generally required to improve the predictive ability of multivariate calibration methods. Pinus brutia Ten. is the most growing pine species in Turkey. Its rotation period is around 80 years; the forest products industry has widely accepted the use of Pinus brutia Ten. because of its ability to grow on a wide range of sites and its suitability to produce desirable products. Pinus brutia Ten. is widely used in construction, window door panel, floor covering, etc. Determination of lignin and extractive content of wood provides information to tree breeders on when to cut and how much chemicals are needed for the pulping and bleaching process. In this study, 58 samples of Pinus brutia Ten. trees were collected in Isparta region of Turkey, and their lignin and extractive content were determined with standard reference (TAPPI) methods. Then, the same samples were scanned with near-infrared spectrometer between 1,000 and 2,500 nm in diffuse reflectance mode, and multivariate calibration models were built with genetic inverse least squares method for both lignin and extractive content using the concentration information obtained from wet standard reference method. Overall, standard error of calibration (SEC) and standard error of prediction (SEP) ranged between 0.35% (w/w) and 2.40% (w/w).     

Recent progress in the chemistry and topochemistry of compression wood

Summary A review of the chemistry and topochemistry of compression wood with 200 references. Compression wood contains on the average 30% cellulose, 35–40% lignin, 10% galactan, 9% galactoglucomannan, 8% xylan, and 2% of a 1,3-glucan (laricinan). The cellulose is less crystalline, and the xylan has fewer arabinose side chains than in normal wood. The lignin is composed of guaiacylpropane and p-hydroxyphenylpropane units. It is more condensed, has a higher proportion of carbon-carbon bonds, and contains fewer arylglycerol--aryl ether structures than a normal conifer lignin. The ray cells and the primary wall of the tracheids have the same chemical composition in normal and compression woods. The galactan is largely located in the outer region of the secondary wall. Only 5–10% of the lignin in compression wood tracheids is extracellular. The middle lamella is less lignified than in normal wood, while the S₁ and inner S₂ layers have a lignin concentration of 30–40% which is twice as high as in normal wood. The lignin content of the S₂ (L) layer is equal to or higher than that of the intercellular region along the wall. The review is concluded with a brief reference to areas where present information is incomplete or lacking.A portion of an Academy Lecture of the International Academy of Wood Science, presented at the International Symposium on Wood and Pulping Chemistry (Ekmandagarna 1981), held in Stockholm, Sweden, June 9–12, 1981. Reprints of the unabridged review, published under the title Recent Progress in the Chemistry, Ultrastructure, and Formation of Compression Wood in the preprints of the symposium (SPCI Report 38, Vol. 1, p. 99–147) are available from the author. I wish to express my gratitude to my colleague Professor Robert A. Zabel for generous travel assistance     

Sorption and thermodynamic properties of wood of <Emphasis Type="Italic">Pinus canariensis</Emphasis> C. Sm. ex DC. buried in volcanic ash during eruption

The hygroscopicity and thermodynamic properties of Pinus canariensis wood buried in volcanic ash, dating from 1100 BC, were studied and compared with recently felled juvenile and mature wood of the same species. The sorption isotherms were obtained by the saturated salt method at 35 and 50 °C. The isotherms were fitted using the Guggenheim–Anderson–de Boer model. The thermodynamic parameters were determined following the Clausius–Clapeyron integration method. To understand the behaviour of each type of wood, the chemical composition, infrared spectra and X-ray diffractograms were determined for each sample. The mature wood has a higher sugar content and lower extractive content than the juvenile and the buried wood. For both temperatures, the isotherm of the mature wood is above the isotherm of the juvenile wood and this, in turn, is above the isotherm of the buried wood, primarily influenced by the higher cellulose and hemicellulose contents and lower extractives content in the mature wood, resulting in a higher number of accessible –OH groups. Degradation of the buried wood due to high temperatures explains why its isotherms are below the isotherms of the recent wood. The energy involved in the desorption process is greater than in adsorption. Similarly, more energy is involved in the mature wood than in the juvenile wood, and the energy involved in the juvenile wood is greater than in the buried wood.     

Reactions between Cr(VI) and wood and its model compounds

Wood, macromolecular and simple model compounds, were reacted with CrO₃ or K₂CrO₄ aqueous solutions. Extracted lignin, guaiacol, vanillin, vanillyl alcohol and homovanillyl alcohol were chosen as model compounds for lignin, whilst cellulose, gum Ghatti, xylan, extracted hemicellulose from pine, methyl-β-D-glucopyranoside and methyl-β-cellobioside were used as models for wood polysaccharides. The kinetics of the reduction reactions of Cr(VI) were monitored using UV-Vis spectroscopy and the results obtained for several temperatures are discussed. In general terms, wood, lignin and lignin model compounds reduced Cr(VI) faster and to a greater extent than polysaccharides or simple sugar molecules. Moreover, lignin model compounds were reduced even faster than lignin. Simple sugars showed a reduction pattern similar to that of cellulose. Extracted hemicellulose revealed to be a poorer reductant while gum Ghatti was the strongest among the polysaccharides. As expected, CrO₃ aq. behaved as a more powerfull oxidant than K₂CrO₄ aq. for these substances. Even at 100 °C, sugars or polysaccharides did not seem to be oxidised by K₂CrO₄ aq. 0.01 M. These results suggest that, because of the differences in reactivity, lignin reacts preferentially when wood is treated with Cr(VI)-containing formulations, like those which are applied in wood preservation treatments.     

Effects of radial growth rate on selected indices for juvenile and mature wood of the Japanese larch

To examine the differences between juvenile and mature wood, 12 aged sample trees from two areas of Nagano Prefecture were harvested; and the radial development of tracheid length, the ring density, and the relation of the radial growth rate (observed by ring width) with some selected indices of ring structure were investigated. The results proved that the radial variation of tracheid length with ring number can be described by a logarithmic formula, and both plantations reached the demarcation of juvenile and mature wood at age 18. With the segmented regression method, we also analyzed radial variation of mean density and found that the demarcation of juvenile and mature wood was at age 15 for sample trees from Saku and at age 21 for those from Yabuhara. By using the results of estimates from juvenile and mature wood based on ring density, we found that high growth rates resulted when producing lower-density wood during the juvenile period, but these rates did not occur during the mature period. The basic reason for this phenomenon is the variation in patterns of earlywood and latewood in juvenile and mature wood, respectively. This result advised us that when managing plantations of Japanese larch it is necessary to take different measurements at different growth periods.