Molecular sieving behavior of carbonized wood: selective adsorption of toluene from a gas mixture containing α-pinene

The adsorption properties of wood carbonized at various temperatures were investigated using a mixed gas containing toluene and α-pinene. Hinoki (Chamaecyparis obtusa) samples carbonized at 500°–1100°C were exposed to gas mixtures of toluene and α-pinene at 20°C. The samples carbonized at 500°–700°C only adsorbed toluene, whereas those carbonized at 800°–1100°C adsorbed both toluene and α-pinene. Analysis of the surface structure of the carbonized wood by nitrogen adsorption at liquid nitrogen temperature indicated that the sample carbonized at 700°C had micropores mainly 0.6 nm in diameter and few mesopores, whereas the samples carbonized at 900°C and 1100°C had mesopores and micropores larger than 0.8 nm in diameter. With the sample carbonized at 700°C, the flat-shaped toluene molecules could probably penetrate into the narrower pores, 0.8 nm in diameter, whereas the bulky globular-shaped α-pinene molecules could not. Carbonization at temperatures higher than 900°C probably enlarged the pore size and thereby reduced the selectivity of adsorption. The results revealed that wood carbonized below activation temperature has a unique flat-pore structure that seems to work as a kind of molecular sieving carbon, successfully removing only the harmful volatile organic compound (VOC), toluene, and leaving behind a pleasant aroma of α-pinene in the atmosphere.     

Effects of heat treatment on brittleness of <Emphasis Type="Italic">Styrax tonkinensis</Emphasis> wood

A new approach is proposed for the evaluation of the brittleness of heat-treated Styrax tonkinensis wood. Heat treatment made wood more brittle when wood was heated at a higher temperature or for a longer time. The brittleness increased to four times that of the control when wood was heated at 200°C for 12 h. For treatment at 160°C, the increase in brittleness without any change in weight is thought to be possibly caused by the relocation of lignin molecules. At higher temperatures, loss of amorphous polysaccharides due to degradation is thought to become the main factor affecting brittleness. The crystallites that were newly formed after 2 h of treatment showed brittleness that was different from that of the inherent crystallites remaining after 12 h of heat treatment. This inherent crystalline cellulose possibly plays a role in brittleness. There is also the possibility of using color to predict the brittleness of heat-treated wood.     

Replication of wood into biomorphous nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor materials

Biomorphous Eu³⁺-doped Y₂O₃ was fabricated by replication of wood templates using vacuum-assisted infiltration of a water-based sol–gel mixture and subsequent calcination at 750°C. The precursor sols were prepared from (Y_0.95Eu_0.05)₂O₃ dissolved in 10 vol% nitric acid and adding citric acid as the chelating agent. X-ray powder diffraction analyses and Rietveld refinements confirmed that the calcined samples were solely composed of bixbyite Y₂O₃:Eu³⁺ phase with a mean crystallite size of 16 nm. Scanning electron micrographs and cathodoluminescence imaging showed that the cellular preform anatomy was retained and that the original wood cell walls were completely transformed into phosphor struts with pore sizes ranging from 5 to 20 μm. The optical properties of the biomorphous phosphor materials were analyzed by photoluminescence spectroscopy and assigned to the characteristic Eu³⁺ (4f⁶ → 4f⁶) electric dipole or magnetic dipole transitions. From fluorescence lifetime measurements, the mean lifetime was calculated as 1.62 ms.     

Elevation difference of Ca<Superscript>2+</Superscript> levels in young leaf cells of bromegrass and induced cold-tolerant enhancement under different controlled chilling temperatures

The changes of Ca2＋ levels in young leaf cells of bromegrass under different controlled chilling temperatures were inves- tigated by an antimonite precipitation cytochemical method. The main results were as follows： under 25/20℃ （day/night） tempera- ture and 14 h photoperiod, electron-dense Ca2＋ antimonite precipitates, indicators of Ca2＋ localization, were mainly localized in the vacuoles, cell walls and intercellular spaces; few Ca2＋ deposits were observed in the cytosol and nuclei. After a 3℃ chilling treatment for 3 h, many Ca2＋ precipitates appeared in the cytosol and nuclei, indicating that Ca2＋ influx had occurred in the cytosol and nuclei. When the 3℃ treatment was prolonged to 8 h, more Ca2＋ deposits appeared in the nuclei and cytosol, but the amount of Ca2＋ deposits in both the cytosol and nuclei decreased markedly after a 24 h treatment and most Ca2＋ deposits were returned to the vacuoles and intercellular spaces after an 8 d treatment. When bromegrass was exposed to 7℃ for 3 h, the Ca2＋ distribution in the cells had no visible changes, compared with that of the 25/20℃ grown control plants. However, when the chilling treatment of 7℃ was prolonged to 8 h, a Ca2＋ influx occurred, where many Ca2＋ deposits were observed in the nuclei and cytosol. More Ca2＋ deposits appeared in the nuclei and cytosol after a 24 h treatment, but the amount of Ca2＋ deposits in the cytosol and nuclei was reduced markedly after an 8 d treatment. After a 14 d treatment, the remaining low level of Ca2＋ was recovered in both the cytosol and nuclei and the Ca2＋ deposits were again located in the vacuoles and the intercellular spaces. The dynamics of subcellular Ca2＋ localization in young leaf cells of bromegrass during a 12℃ chilling treatment were similar to those of the 7℃ treatment. Besides, the results showed that the frost tolerance ofbromegrass exposed to 3℃ for 8 d increased by 6℃, for 7℃ and 8 d by 4℃ and for 12℃ and 14 d by 3℃, compared with the controls.     

Effects of carbonization temperatures on microstructure of carbon fiber precursors prepared from liquefied wood

In order to enlarge the utilization field of wood and decrease the costs of carbon fibers, carbon fiber precursors from liquefied wood were prepared by soaking liquefied wood in a solution containing hydrochloric acid and formaldehyde, after melt-spinning by adding hexamethylenetetramine. The microstructure evolution of the precursor during carbonization was studied by FTIR, X-ray analysis and Raman spectroscopy. The results show that precursors from liquefied wood above 400°C had diffraction peaks corresponding to the (100) crystal plane. When the carbonization temperature reached 500°C, Raman spectroscopy showed the D peak at wave number of 1360 cm–1 and the G peak at 1595 cm–1. By increasing the carbonization temperature, the microstructure of the precursors became more ordered. Although the structure of the precursor changed at 500 and 800°C, the peaks at 1632 and 1454 cm–1 corresponding to the characteristic vibrations of aromatic rings, remained during carbonization. This implies that the precursor from liquefied wood cannot be easily formed into graphite.     

Modeling of simultaneous unidirectional leaching and reduction of Cr<Superscript>6+</Superscript> in unfixed CCA treated wood

The unidirectional leaching of unfixed hexavalent chromium (Cr⁶⁺) from wood freshly treated with chromated copper arsenate (CCA) is modeled as simultaneous diffusion and first-order chemical fixation reaction. Small wood specimens were coated to restrict preservative movement to one direction, then treated with CCA and immersed in water to evaluate unidirectional leaching characteristics. The directional diffusion coefficients and reaction rate constants of Cr⁶⁺ in unfixed CCA-treated red pine (Pinus resinosa Ait.) and southern pine (Pinus sp.) were estimated by least squares fitting of the model to leaching results in each direction independently. The reaction rate constants calculated from the diffusion and leaching model were generally consistent with results from pure fixation experiments, although the computed rate constants increased under the most severe longitudinal leaching conditions. The applicability of using diffusion coefficients and rate constants estimated from leaching results was tested using a finite difference implementation of the diffusion and reaction model to predict unidirectional leaching from small samples immersed intermittently in water. The predicted leachate quantities were consistent with experimental measurements at the end of each of five leaching events of various durations at temperatures alternating between 13 and 23°C over a 9-day period.     

Nickel-catalyzed carbonization of wood for coproduction of functional carbon and fluid fuels I: production of crystallized mesoporous carbon

Japanese larch wood loaded with nickel (1%–4%) alone or with nickel and calcium (0.25%–1.5%) was carbonized at 800°–900°C for 0–120min with a heating rate of 5°–20°C min⁻¹ in a helium flow of 5.8−46.4 ml STP cm⁻² min⁻¹ to examine the influence of these variables on the crystallization of carbon (the formation of T component) and the development of mesoporosity. From the obtained results, reaction conditions suitable for effective production of carbon with the dual functions of adequate electroconductivity and adsorption capacity in liquid phase were established, thereby explaining the factors that govern the process. It was also confirmed that mesopore having a diameter of about 4 nm was selectively produced at the cost of specific (BET) surface area in parallel with the formation of T component. This result provided good insight into how the simultaneous dual function could be realized.     

Carbonization mechanism of bamboo（phyllostachys） by means of Fourier Transform Infrared and elemental analysis

Bamboo was carbonized at different temperatures ranging from 200℃ to 600℃.The dependence of the change of hemicellulose,cellulose,and lignin on the temperature was investigated by means of elemental analysis and Fourier Transform Infrared (FTIR) spectra of the residual solid products.The results showed:(1)Below 200℃,hemicellulose in bamboo wasdecomposed and a large amount of hydroxyl groups are dislocated from hemicellulose and cellulose,accompanied by the evolution of water to escape.(2)200℃-250℃,cellulose in bamboo was brastically decomposed whereas the net structure of lignin keep stable,with the except of the dislocation of methoxyl groups from lignin.(3)250℃-400℃,the net structure of lignin collapse,up to 400℃,followed by that the more position in aryl groups are substituted.(4)For bamboo carbonization,the aromatization of residual carbon has approximately completed at the temperature as high as 600℃.But the fusion of aromatic rings possibly does not occur.     

Screening for condensed tannin-degrading fungi with a synthetic <Superscript>14</Superscript>C-labeled compound

To find fungi that are potent for degradation of condensed tannin, a two-step screening was used. This involved measurement of fungal growth rate on Japanese cedar (Cryptomeria japonica) bark, followed by determination of [¹⁴C]-labeled CO₂ generated from fungal degradation of synthetic [¹⁴C]-labeled condensed tannin model. In the first screening, 75 strains of wood rot fungi were tested, and 19 strains effectively decreased bark weight and/or the weight of the methanol-soluble fraction. For the second screening, [¹⁴C]-labeled condensed tannin model compound was synthesized in 11.8% yield based on radioactivity measurements. Over the incubation period, Coriolus hirsutus K-2671, Lentinus edodes Is, and Lampteromyces japonicus Nn showed higher cumulative [¹⁴C]-labeled CO₂ emissions than the other strains and mineralized the [¹⁴C]-labeled condensed tannin model compound by 3.7%, 3.0%, and 3.0%, respectively. Fractionation of the methanol extracts from the medium by gel permeation chromatography after fungal treatment suggested that fungi that can induce the emission of significant levels of [¹⁴C]-labeled CO₂ can extensively depolymerize condensed tannins.     

Relationship between <Superscript>137</Superscript>Cs concentration and potassium content in stem wood of Japanese cedar (<Emphasis Type="Italic">Cryptomeria japonica</Emphasis>)

To utilize forest resources in areas affected by fallout from the Fukushima Daiichi Nuclear Power Plant accident, it is important to understand the mechanisms of ¹³⁷Cs movement through the stem wood of contaminated trees. Understanding the mechanism of absorption and migration of ¹³⁷Cs to stem wood is necessary for clues to the future prediction of the transition of ¹³⁷Cs to xylem. In the present study, radial variations in ¹³⁷Cs concentration were investigated in Japanese cedar (Cryptomeria japonica D. Don) trees collected 1 year and 10 months after the accident. Additionally, the relationship between ¹³⁷Cs concentration and potassium (K) content was established. Trees with a higher moisture content and lower lightness value in heartwood tended to have a higher ¹³⁷Cs concentration in the heartwood. In these trees, ¹³⁷Cs concentration peaked at the heartwood–sapwood boundary and gradually decreased toward the pith. By contrast, K content within the heartwood remained nearly constant along the radial direction. The heartwood-to-sapwood ratio of ¹³⁷Cs concentration was significantly positively correlated with that of K content. Based on these results, we suggest that ¹³⁷Cs movement from sapwood to heartwood might be related to the K content ratio of heartwood and sapwood.     

冷湿层积法对印度冷杉(Abies pindrow)和长叶云杉(Picea smithiana）种子萌发的影响

研究赤霉素(GA3),冷湿和温度 对五个种源的印度冷杉(Abies pindrow)和长叶云杉(Picea smithiana)种子萌发的影响.种子被浸泡在GA3 (10 mg(L-1)中24小时,然后在3(5(C温度的条件下冷藏15天.设计4个温度(10(C, 15(C, 20(C 和 25(C)条件来促进种子的萌发.结果表明,浸泡和冷湿处理明显增加种子的萌发率.在10 (C时种子的萌发率最高.总体结果表明,种子被浸泡在GA3 (10 mg(L-1)中24小时,冷湿藏15天,可以有效地促进印度冷杉和长叶云杉的种子萌发.统计数据表明,浸泡处理、温度和种源以及与温度的相互作用都对种子的萌发有明显的影响.     

Diamond and pore structure observed in wood charcoal

Conclusions Various carbon structures were observed in the wood charcoal sample: the well known pyrolytic graphite layers, onion-like particles, and diamond structure. It is suggested that wood charcoal carbonized at 700°C is a complex of various carbon structures. The pore structure was observed by electron microscopy, and it is supposed that the microstructure and pores are closely related. Further study of the microstructure during the carbonization process of charcoal is necessary to better understand the characteristic functions of wood charcoal for utilizing it as a source of carbon material.A summary of this study was presented at the 51st annual meeting of the Japan Wood Research Society, Tokyo, April 2001, and the 50th annual meeting of the Society of Materials Science, Osaka, May 2001     

Study on the effect of nano-silver impregnation on mechanical properties of heat-treated <Emphasis Type="Italic">Populus nigra</Emphasis>

The present study is aimed at investigating the effect of heat treatment of nano-silver-impregnated Populus nigra on weight loss, modulus of rupture (MOR), modulus of elasticity (MOE), and compression parallel to grain. Specimens were impregnated with 200 PPM water-based solution of nano-silver particles at 2.5 bar in a pressure vessel. For heat treatment, both nano-silver-impregnated and simple specimens were kept for 24 h at 45°C and then further for 24 h at 145°C and finally for 4 h at 185°C. MOR decreased from 529 to 461 kg/cm² in heat-treated specimens; MOE and compression parallel to grain were though improved. Also, comparison between heat-treated and nano-silver-impregnated heat-treated specimens showed that there was a decrease in MOR and MOE in nano-silver-impregnated heat-treated specimens. This shows that nano-silver impregnation facilitates transfer of heat in wood and it may increase the process of degradation and pyrolysis of wood structures in deeper parts of specimens.     

Influence of carbonization temperature on the anatomical characteristics of Ocotea porosa (Nees & Mart. Ex Nees) L. Barroso

The carbonization process causes different physical and chemical transformations to wood, affecting the final properties of the charcoal produced. In Brazil, the cutting and use of Ocotea porosa (Nees & Mart. Ex Nees) L. Barroso is legally prohibited. But the difficulty of identifying the species used to produce charcoal hinders enforcement efforts to protect this and other endangered tree species. The aim of this work was to characterize the anatomy of charcoal made from O. porosa at different temperatures to provide information to facilitate differentiation of the species by the authorities in charge of suppressing illegal commerce. Samples were carbonized by direct heating and final temperatures of 350, 450 and 650 °C, besides a group under a ramp heating regime also with a final temperature of 450 °C. The qualitative characteristics of the O. porosa wood were preserved at the carbonization temperatures studied permitting the use of its anatomical structures for identification of carbonized wood to support control of the illegal trade in charcoal of this species.     

Intercalation of wood charcoal with sulfuric acid

Intercalation of wood charcoal with sulfuric acid (H₂SO₄) was investigated. Carbonized sugi (Japanese cedar) samples were prepared by heating at various temperatures in the range 1700°–2700°C. Electrochemical oxidization was carried out in H₂SO₄ and the feasibility of intercalation was determined. In potentiometric analysis, plateaus appeared for samples carbonized at temperatures above 2300°C. In their X-ray diffraction profiles, the peak at around 26° was shifted to a smaller angle of about 22.4°. These results can be considered as signs of intercalation with acid molecules. Fourier transform infrared analysis of charcoal heated at 2700°C, following washing with water and drying of the sample, showed a band at 1220 cm⁻¹ that was assigned to a sulfonate group. This band was not observed for samples heated at 1900°C. These observations suggest the occurrence of intercalation in the former charcoal, but not in the latter. It is concluded that wood charcoal can undergo intercalation when it has ordered stacking of hexagonal carbon layers. Part of this article was presented at the 55th, 56th, and 57th Annual Meetings of the Japan Wood Research Society, Akita, Hiroshima, and Tsukuba, August 2006, August 2007, and March 2008, respectively, and at the International Conference on Carbon “CARBON 2008,” Nagano, July 2008     

Variation in carbon concentration and wood density for five most commonly grown native tree species in central highlands of Ethiopia: The case of Chilimo dry Afromontane forest

ABSTRACT

Information regarding carbon concentration and wood density are lacking in Chilimo dry Afromontane forest.

The aim of this study was to estimate carbon concentration and wood density for Allophyllus abyssinicus, Olea europaea, Olinia rochetiana, Rhus glutinosa, and Scolopia theifolia. A total of 105, 30–50 mm thick wood discs were collected and oven dried at 102°C and 67°C to constant weight, chopped and finally grinded into 0.2 mm with a grinding mill. Carbon concentration was analyzed using the ash method, while wood density was estimated using the water displacement method. The highest carbon concentration (57.12%) was found for O. rochetiana, however, the lowest carbon concentration (56.43%) was found for A. abyssinicus. Stem parts had higher carbon concentration (56.98%) than branch (56.74%) and leave (54.53%) parts. O. europaea exhibited the highest wood density (0.67 g cm^?3) value than other species. However, the lowest wood density (0.42 g cm^?3) was exhibited for A. abyssinicus. Wood density was also showed a decreasing trend along with increases in stem height and maximum wood density (0.62 g cm^?3) was found under stump position, while, the minimum wood density (0.4 g cm^?3) was found under tree commercial height.     

Dielectric properties of copper-ethanolamine treated Chinese fir (Cunninghamia lanceolata Hook.)

In order to clarify the interaction between copper and wood substances in wood treated with copper containing water-borne wood preservatives, the dielectric constant ε′ and dielectric loss factor ε″ of untreated wood and wood treated with four concentration levels of copper-ethanolamine (Cu-EA) solutions were determined within a temperature range from –100 to 40°C and a frequency range from 100 to 1 MHz. Three dielectric relaxation processes were observed in the ε″ spectrum; among them R-I is based on the reorientation of methylol groups in the amorphous region of wood cell walls and R-II is related to wood extractives. R-III appeared in Cu-EA treated wood, and its magnitude decreases with the concentration of Cu-EA solutions used in this experiment. This relaxation process was considered to be based on the reorientation of copper-ethanolamine-wood complexes in wood cell walls. At low copper retention, the hydrogen in the complex can form hydrogen bonding with adjacent hydroxyl groups, which results in a strong bonding state between copper and wood; at high copper retention, the numerous copper-ethanolamine complexes not only hinder them from forming hydrogen bonding with adjacent wood molecules due to steric hindrance, but also weaken the interaction between wood molecules themselves, which corresponds to reducing ε″ values of both R-I and R-III processes. The results explain the fact of in-creasing copper leaching in wood treated with high concentration copper-based water-borne preservatives.     

Fire performance of carbonized medium density fiberboard manufactured at different temperatures

Authors established a new manufacturing technology for crack-free carbonized boards by pressing and carbonizing the medium-density fiberboard. Industrialization of new functional carbon materials was performed by investigating the fundamental properties of the carbonized boards. To be used as a construction material, the carbonized board needs to satisfy the fire performance regulation. In this study, the carbonized boards were manufactured from medium-density fiberboard (c-MDF) at different temperatures and then fire performance including flame retardancy and smoke toxicity was analyzed using a cone calorimeter and noxious gas analyzer. The results show that as the carbonization temperature increases, weight loss ratio decreases and flame retardancy increases. In the c-MDF at 800 and 1000 °C, no external damage was observed after combustion. These c-MDFs satisfy the total heat release (standard below 8 MJ/m²) and heat release rate (standard below 200 kW/m²) regulations according to the Building Standard Law of Korea and Japan. In addition, the c-MDFs showed the lower total smoke release (TSR, 0.213 m²/m²) than that of virgin MDF (94.281 m²/m²). The c-MDF at 800 and 1000 °C were, therefore, classified as a class III flame retardancy material and can be used as indoor finishing material.     

Three-source partitioning of soil respiration by <Superscript>13</Superscript>C natural abundance and its variation with soil depth in a plantation

Partitioning soil respiration into three components is vital to identify CO₂ sink or source and can help us better understand soil carbon dynamics. However, knowledge about the influences of soil depth and the priming effect on soil respiration components under field has been limited. Three components of soil respiration (root respiration, rhizomicrobial respiration and basal respiration) in a plantation in the hilly area of the North China were separated by the ¹³C natural abundance method. The results showed that the average proportions of rhizomicrobial respiration, root respiration and basal respiration at the 25–65 cm depths were about 14, 23 and 63 %, respectively. Three components of soil respiration varied with soil depth, and root respiration was the main component of soil respiration in deeper soil. The priming effect was obvious for the deep soil respiration, especially at the 40–50 cm depth. Thus, depth and priming effect should be taken into account to increase the accuracy of estimations of soil carbon flux.     

Anthropogenic disturbance of natural forest vegetation on calcareous soils alters soil organic matter composition and natural abundance of <Superscript>13</Superscript>C and <Superscript>15</Superscript>N in density fractions

In the last century, many calcareous soils in Castilla León (northwestern Spain) have been transformed from natural Quercus ilex forest to cropped land. Reforestation with Pinus halepensis has been taking place during the past 40 years. In order to obtain a better understanding of how these disturbances affect ecosystem functioning, we studied the quantity and quality of soil organic matter (SOM) in natural forest ecosystems, cropland and Pinus plantations. Density fractionation combined with ultrasonic dispersion enables separation and study of SOM fractions: free organic matter (OM), OM occluded into aggregates and OM stabilized in organo-mineral complexes, considered on the basis of the type of physical protection provided. We separated SOM density fractions and determined the concentrations of C and N, C/N ratios and the natural isotopic abundance (δ¹³C and δ¹⁵N values). Transformation of Quercus forest to cropland resulted in major losses of SOC and N, as expected. However, subsequent reforestation with Pinus resulted in good recovery of the original SOC and soil N pools. This indicates the potential for enhanced C storage in agricultural soils by their reversion to a forested state. Study of the density fractions and their ¹³C and ¹⁵N signatures enabled better understanding of the high stability of OM in calcareous soils, and analysis of δ¹³C variations throughout the profile also enabled identification of past C3/C4 vegetation change. Despite the different OC contents of soils under different land use, OM stabilization mechanisms were not significantly different. In calcareous soils, accumulation of SOC and N is mainly due to organo-mineral associations, resulting in physicochemical stabilization against further decomposition.