TGA modeling of the thermal decomposition of CCA treated lumber waste

 To guide the development of thermal decomposition methods for disposal of CCA treated wood, reactions during the thermal decomposition of CCA treated wood were modeled using thermogravimetric analysis (TGA), with special focus placed on arsenic volatilization. Simple inorganic compounds, such as As₂O₅, CuO, and Cr₂O₃, were used to model the thermal behavior of the inorganics in CCA treated wood. In air and nitrogen, arsenic (V) oxide began to volatilize at 600 °C during temperature ramps at 5 °C/min. During a 5 °C/min ramp in a hydrogen mix, arsenic (V) oxide began decomposition at 425 °C. Arsenic volatile loss from CCA treated wood can depend strongly on the gases produced by wood thermal decomposition. In the presence of As₂O₅, chromium (III) oxide and copper (II) oxide formed arsenates in air and nitrogen. Chromium arsenates began decomposition as low as 790 °C. This suggested that chromium arsenates in CCA treated wood formed during original preservative fixation may decompose as low as 790 °C. Copper arsenates were stable up to 900 °C in air, but showed only a limited range of stability in nitrogen. Depending on process conditions, the formation of copper arsenates may limit arsenic loss during thermal decomposition of CCA treated wood up to 900 °C. The thermal decomposition of inorganic oxides was influenced by interactions with wood and wood decomposition products. In a dry YP sawdust/As₂O₅ mix, arsenic (V) oxide volatilized at 370 °C during inert pyrolysis at 5 °C/min and at 320 °C during smoldering combustion at 5 °C/min. Thermal dwells of a dry YP/As₂O₅ mix showed no arsenic loss at 250 °C, but significant loss occurred during higher temperature dwells. During inert pyrolysis at 5 °C/min, the formation of complexes and hydrates were shown to prevent arsenic loss up to 400 °C. Received 14 July 1999     

Effect of extractives on conferred and natural durability of Cupressus lusitanica heartwood

? Identification of extractives present in Cupressus lusitanica heartwood has been conducted using GC-MS analyses. The chromatogram of toluene/ethanol extracts indicated the presence of large amounts of benzaldehyde and numerous terpenic compounds such as cedrol, agathadiol, epimanool, bornyl acetate, α-cedrene and β-cedrene.

? The effect of these extractives on the natural durability of cypress wood was investigated on heart wood blocks exposed to pure culture of Poria placenta before or after solvent extraction. Weight losses revealed severe fungal degradations on the extracted blocks compared to unextracted ones.

? Efficiency of heartwood extractives as inhibitors of the growth of Poria placenta on malt/agar test confirms their contribution to cypress natural durability.

? Cypress blocks were treated at 240 °C for different times to reach different levels of thermodegradation to evaluate effect of heat treatment on fungal durability. Results indicate that evaporation of volatile extractives during the first few minutes of heat treatment contribute to decreased wood durability, while longer treatment times lead to the expected improvement of durability.

? This study suggests that the content of extractives, which may be modified during wood drying or weathering processes, could be the origin of the conflicting data described in the literature concerning cypress natural durability.

     

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.     

Influence of accessory substances,wood density and interlocked grain on the compressive properties of hardwoods

Wood samples of nine tropical hardwoods from Peru and sugar maple wood from Quebec were selected to perform moisture sorption tests associated with parallel-to-grain and tangential compression tests using a multiple step procedure at 25°C. Cold-water and hot-water extractives, sequential cyclohexane (CYC), acetone (ACE) and methanol (MET) extracts, ash content (ASH), wood density and interlocked grain (IG) were evaluated on matched samples too. Wood density corrected for the accessory substances was by far the major factor positively affecting the compressive properties of tropical hardwoods. The total amount of accessory substances is required in order to establish better relationships between physico–mechanical properties and density of tropical hardwoods. For a given wood density, the ultimate stress in parallel-to-grain compression was higher in tropical hardwoods than in temperate hardwoods. However, the compliance coefficients for both types of woods were quite similar. Sequential extraction with organic solvents was the most suitable method for evaluating the effect of extractives on compressive properties of tropical hardwoods. The CYC and ACE fractions did not contribute to variation in these mechanical properties. The substances dissolved in MET affected positively the compliance coefficient s ₁₁ in parallel-to-grain compression and negatively the compliance coefficient s ₃₃ in tangential compression. The IG decreased the compliance coefficient s ₁₁ but also decreased the ultimate stress in parallel-to-grain compression. Finally, variations in compressive properties that were due to changes in equilibrium moisture content (EMC) were clearly influenced by wood density; denser woods were more sensitive to changes in EMC than lighter woods.     

Effects of high temperature kiln drying on the practical performances of Japanese cedar wood (Cryptomeria japonica) I: changes in hygroscopicity due to heating

The effect of heating on the hygroscopicity of Japanese cedar wood was investigated as a simple evaluation of thermal degradation in large-dimension timber being kiln-dried at high temperatures (>100°C). Small wood pieces were heated at 120°C in the absence of moisture (dry heating) and steamed at 60°, 90°, and 120°C with saturated water vapor over 2 weeks, and their equilibrium moisture contents (M) at 20°C and 60% relative humidity (RH) were compared with those of unheated samples. No significant change was induced by steaming at 60°C, while heating above 90°C caused loss in weight (WL) and reduction in M of wood. The effects of steaming were greater than those of dry heating at the same heating temperature. After extraction in water, the steamed wood showed additional WL and slight increase in M because of the loss of water-soluble decomposition residue. The M of heated wood decreased with increasing WL, and such a correlation became clearer after the extraction in water. On the basis of experimental correlation, the WL of local parts in large-dimension kiln-dried timber was evaluated from their M values. The results indicated that the thermal degradation of inner parts was greater than that of outer parts.     

Chemical emissions from adhesive-bonded wood products at elevated temperatures

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to examine the chemical emissions from the glued wood samples at elevated temperatures (150, 200, 250, 300, 350, 400, 450, and 500°C). Two wood species, Douglas-fir (Pseudotsuga menziesii) and southern pine (Pinus palustris), one structural adhesive, phenol–resorcinol–formaldehyde (PRF), PRF-bonded Douglas-fir, and PRF-bonded southern pine were evaluated. The volatile compounds with a mass range of 35–300 m/z emitted from the pyrolysis samples were separated by gas chromatography (GC) and identified by mass spectrometry (MS). The results indicated that compared to neat wood and resin film samples, several additional pyrolysis products were observed for the PRF-bonded wood samples including (1) acetaldehyde and butanedial for PRF-bonded Douglas-fir and (2) acetaldehyde, furfural, 2-furanmethanol, butanedial, 2,3-butanedione, cyclopropyl carbinol, 1,2-benzenediol, and 1-(acetyloxy)-2-propanone for PRF-bonded southern pine. These additional compounds were possibly associated with the interaction between wood and PRF resin. The results also indicated that bonded wood products would be less thermally stable than those of neat wood and PRF resin samples.     

Effect of major inorganic nutrients on <Emphasis Type="Italic">β</Emphasis>-thujaplicin production in a suspension culture of <Emphasis Type="Italic">Cupressus lusitanica</Emphasis> cells

 The optimum conditions for β-thujaplicin production in a Cupressus lusitanica cell suspension culture were investigated. The conditions required for β-thujaplicin production were clearly different from the conditions for cell growth. The initial phosphate concentration and pH did not affect β-thujaplicin production. A total nitrogen source concentration higher than 3.2 mM suppressed production due to the presence of the ammonium ion. β-Thujaplicin production was observed at 95 mg/l without adding the ammonium ion to the medium. Strict control of major inorganic nutrients was not necessary to produce β-thujaplicin. This finding seems to be favorable for future automated production of β-thujaplicin in commercial cell culture plants.     

Chemistry and ecotoxicity of heat-treated pine wood extractives

Pine (Pinus pinaster) wood was heat-treated in an autoclave for 2?C12?h at 190?C210°C. Hemicelluloses were the first compounds affected by the treatment. In general, the sugar decrease was higher for arabinose and galactose followed by xylose and mannose. Lignin started to degrade for small mass losses but at a slower rate than hemicelluloses, and cellulose only degraded significantly for severe treatments. Almost all of the original extractives disappeared, and new compounds arose such as anhydrosugars and phenolic compounds. The compounds that might leach from heat-treated wood were mainly those identified in the water and ethanol extracts, all of which were not harmful at the existing concentrations, thereby reinforcing the wood heat treatment as an environmental benign process.     

An investigation on the transition characteristics of the wood cell walls during carbonization

The structural changes of the cell wall and crystalline cellulose of Quercus variabilis wood in a pyrolysis system at several temperatures ranging from 250 to 500°C were investigated to examine the wood carbonization characteristics. The volume of the wood sample was decreased and the weight loss was increased by increasing the carbonization temperature. Vessels collapsed severely in tangential direction during the charring process above 350°C. SEM observation indicated that the layering structure of the walls in wood fibers and parenchyma cells were retained below 300°C. However, the cell walls above 350°C changed to an amorphous-like structure without cell wall layering. X-ray diffraction confirmed that the cellulose crystalline substance was still remained at the carbonization temperature of 300°C but was not detected above 350°C. It can be concluded that the transition from Q. variabilis wood to charcoal might occur at approximately 350°C.     

Cell growth and nutrient uptake by cell suspensions of <Emphasis Type="Italic">Cupressus lusitanica</Emphasis>

 Conditions for cell growth of suspension cultures of Cupressus lusitanica, which has high β-thujaplicin productivity, were studied. The medium that provided the highest growth rate was IS-1 medium (pH 5.5), modified from Gamborg B5 medium containing 32 mM of total nitrogen. Its NO₃-N/NH₄-N ratio was 30 : 2. The maximum growth represented a 25-fold increase over the initial biomass on a fresh weight basis after 30 days of culture in this medium. The highest cell growth was obtained with an initial pH of 3.5–5.5, but the pH of the medium settled to about pH 4.0 from any of the initial pH values in this report. The cells cultured under this condition were able to produce a high level of β-thujaplicin. Received: September 7, 2001 / Accepted: May 7, 2002 Present address: Teijin Ltd., Ehime 791-8530, Japan Present address: Q'SAI Co. Ltd., Fukuoka 811-3422, Japan Part of this report was presented at the 10th international symposium on wood and pulp chemistry, Yokohama, Japan, June 1999 Correspondence to:K. Fujita     

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 high temperature kiln drying on the practical performances of Japanese cedar wood (Cryptomeria japonica) II: Changes in mechanical properties due to heating

Japanese cedar wood specimens were steamed at 80°, 100°, and 120°C over 14 days, and their equilibrium moisture content (M) at 20°C and 60% relative humidity, longitudinal dynamic Young’s modulus (E), bending strength (σ _max), and breaking strain (ε _max) were compared with those of unheated specimens. Steaming for a longer duration at a higher temperature resulted in a greater reduction in M, σ _max, and ε _max. The E of wood was slightly enhanced by steaming at 100°C for 1–4 days and 120°C for 1–2 days, and thereafter it decreased. The slight increase in the E of sapwood was attributable to the reduction in hygroscopicity, while sufficient explanation was not given for a greater increase in the heartwood stiffness. Irrespective of the steaming temperature, the correlations between M and the mechanical properties of steamed wood were expressed in terms of simple curves. M values above 8% indicated a slight reduction in E and s max, whereas M values below 8% indicated a marked decrease in the mechanical performances. In addition, the e max decreased almost linearly with a decrease in the value of M. These results suggest that hygroscopicity measurement enables the evaluation of degradation in the mechanical performances of wood caused by steaming at high temperatures.     

Emissions of volatile organic compounds from heated needles and twigs of <Emphasis Type="Italic">Pinus pumila</Emphasis>

A study was conducted to explore the mechanism that emissions of volatile organic compounds(VOC) from heated needles and twigs(200°C,within 15 min) of Pinus pumila affect fire behaviours using the technology of Thermal Desorption-Gas Chromatography-Mass Spectrometry(TD-GC-MS).The results indicated that the main components of VOC from heated needles and twigs are terpenoids.Most of these terpenoids are monoterpenes.Terpenoids account for 72.93% for the needles and 92.40% for the twigs of the total VOC,and their emission ratios are 61.200 μg·g-1 and 217.060 μg·g-1 respectively.Heated twigs can emit more terpenoids than heated needles because twigs had more volatile oils than needles.In actual fires,these large amounts of terpenoid emissions,especially the monoterpene emissions,have strong effects on fire behaviors that are not only in the initial stage but also in the fast propagation stage of fires.These flammable gases are capable of causing violent combustion and creating crown fires.In addition,if these gases accumulate in an uneven geographical area,there will be a possible for eruptive fires and/or fires flashover to occur.     

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.     

Bondability of tropical fast-growing tree species III: curing behavior of resorcinol formaldehyde resin adhesive at room temperature and effects of extractives of <Emphasis Type="Italic">Acacia mangium</Emphasis> wood on bonding

The effects of curing time at room temperature and methanol extracts from Acacia mangium on the curing behavior of resorcinol formaldehyde (RF) adhesive were examined by using the thermomechanical analysis spring method. For a specimen that was cured for 3 months at room temperature, the relative elasticity (E _r) curve did not change to a hard glass state from room temperature to 200°C and the adhesive had cured completely. The initial temperature of the reactive zone for chemical and mechanical changes was 15° and 25°C higher than that for the control when 10 and 15 parts by weight methanol extract was added to the liquid adhesive, respectively. It appears that the extractives of A. mangium in RF adhesive interferes with the chemical cure of the adhesive. It is suggested that a combination of curing time and sweeping by methanol on the laminae surface can improve the bonding performance of A. mangium laminates bonded with RF at room temperature.     

Colour responses of black locust (Robinia pseudoacacia L.) to solvent extraction and heat treatment

The colour parameters (CIE L*a*b*) of black locust (Robinia pseudoacacia L.) wood meals extracted with seven solvents and heated under saturate vapour at 120°C are measured and the UV–vis spectrum analysis of dioxane extractives is performed to investigate the influence of extraction and thermal treatment on wood discolouration. The results show that extractions with polar solvents such as water, ethanol and dioxane can cause substantial decrease of b* but have little effect on a* and that extractions with less or non-polar solvents such as chloroform, ether and hexane can hardly influence both a* and b*. Extractions with ethanol and dioxane can also increase the optical reflection (L*) and arise a higher ΔE change than that with less or non-polar solvents. Heat treatment has much more influence on colour parameters than extractions do. After heat treatment, the lightness index of all the samples declines but a* value increases. The discolouration during thermal treatment is mainly due to the existence of polar extractives. Tannins, flavonoids and hydroxyanthraquinones are found in the dioxane extractives. The heated dioxane extractives have an obvious absorption between 400 and 600 nm. The condensation of the tannin molecules and the oxidation of the hydroxyl groups in flavonol molecules make up the potential reason of the formation of new colour substances during heat treatment. The elimination of the dioxane extractives can effectively reduce the extent of thermally induced discolouration.     

Extraction of betulin from bark of Betula platyphylla by supercritical carbon dioxide extraction

Betulin, which is a medicinal pentacyclic triterpene, is abundant in the bark of white birch (Betula platyphlly). The bark of birch was collected at Tayuan Forest Farm of Jiagedaqi, Heilongjiang Province in September 2000. Supercritical fluid extraction (SFE) that is a new separation technology has been used for the processing pharmaceutical and natural products. In this paper, the extraction of betulin from the bark of birch by supercritical CO2 extraction was studied. The authors investigated and analyzed a few parameters such as modifier dosage, extraction pressure and extraction temperature. The optimal extraction conditions showed that the modifier dosage used for per gram bark powder was 1.5 mL, the extraction pressure was at 20 Mpa, and the extraction temperature was at 55 ℃. The velocity of flow of liquid CO2 was at 10 kg/h. The pressure and temperature in separation vessel were at 5.5 Mpa and 50 ℃, respectively.     

Effects of temperature on mechano-sorptive creep of delignified wood

The effects of temperature on mechano-sorptive (MS) creep of delignified hinoki wood (Chamaecyparis obtusa Endl.) were investigated using longitudinal (L) and radial (R) specimens during adsorption and desorption over the temperature range of 20°–80°C. The results were compared with those of stepwise delignified specimens tested at a constant temperature of 20°C. It was found that the effects of temperature on the MS creep of delignified specimens are more remarkable than for untreated specimens. The tendencies of increasing MS creep with temperature, delignification, and their combination were observed. The increase in MS creep for L specimens was relatively small and almost equal in both adsorption and desorption processes, while for R specimens the MS creep was small in desorption, but significantly different in adsorption. In addition, good correlation was observed between the MS coefficient (K) and instantaneous compliance (J ₀). The increase in MS creep occurs as a result of temperature increase or decrease in lignin content, or their interacting effects. However, in the case of desorption for R specimens, the increase of MS creep was unexpectedly small due to a remarkably increased J ₀. Part of this report was presented at the 15th Annual Meeting of the Chubu Branch of the Japan Wood Research Society in Fukui, October 2005     

Wood properties of juvenile and mature heartwood in Robinia pseudoacacia L.

The aim of this study is to characterise the properties of juvenile and mature heartwood of black locust (Robinia pseudoacacia L.). Content, composition and the subcellular distribution of heartwood extractives were studied in 14 old-growth trees from forest sites in Germany and Hungary as well as in 16 younger trees of four clone types. Heartwood extractives (methanol and acetone extraction) were analysed by HPLC-chromatography. UV microspectrophotometry was used to topochemically localise the extractives in the cell walls. The natural durability of the juvenile and mature heartwood was analysed according to the European standard EN 350-1. Growth as well as chemical analyses showed that, based on extractives content, the formation of juvenile wood in black locust is restricted to the first 10–20 years of cambial growth. In mature heartwood, high contents of phenolic compounds and flavonoids were present, localised in high concentrations in the cell walls and cell lumen of axial parenchyma and vessels. In juvenile wood, the content of these extractives is significantly lower. Juvenile wood had a correspondingly lower resistance to decay by Coniophora puteana (brown rot fungus) and Coriolus versicolor (white rot fungus) than mature heartwood.