Dielectric relaxation due to the heterogeneous structure of wood charcoal

Delignified hinoki wood and cellulose as well as hinoki and lauan woods were carbonized at 590°C for 1 h. The dielectric properties of these specimens were measured at 20°C in a frequency range of 20 Hz to 1 MHz. Inflection points in the dielectric constant (ε′) versus the logarithm of frequency (log f) curves as well as in the logarithm of the electric conductivity (log σ) versus log f curves for all specimens prepared were recognized. Peaks in the dielectric loss and the imaginary part of the complex conductivity versus the log f curves were detected in the frequency location corresponding to the inflection point in the ε′ and log σ versus log f curves. It was considered that this relaxation was responsible for the interfacial polarization observed in heterogeneous materials because no permanent dipoles existed in the specimens carbonized above 500°C. The Cole–Cole circular arc law was applied to account for this relaxation. Similar average relaxation times were obtained for all specimens. These results suggested that the observed relaxation was ascribed to interfacial polarization at microscopic levels in the cell walls.     

The diffusion, size and location of added silver grains in the cell walls of Swedish pine, Pinus sylvestris

The size and location of silver particles in K-glycerate/AgNO₃ impregnated Swedish pine, green wood as well as high temperature dried, have been studied using TEM micrographs. The diameter of the silver particles was found to be 2–20 nm in the impregnated green wood and as large as 1000 nm (major axis) for the ellipsoid-shaped silver clusters in the impregnated dried wood. Studying the projected area of the silver particles in impregnated green wood indicated that there are a lot of particles (40%) in the compound middle lamella with fewer particles in the S₂ (6–8%), S₁ (4%) and S₃ (2%) layers. The average distance between the silver particles, 50 nm (S₂-layer), in impregnated green wood shows that the impregnant is distributed in the cell wall at the microfibrilar level. Experimental results show that the fastest diffusion path into the cell wall is from the lumen over the pit membrane through the compound middle lamella and not from the lumen through the secondary wall layer S₃. Received 11 January 1998     

Turbulence in the wood system with small and short stresses

Small compressive stresses (500 N, 1000 N, 2000 N) of small duration were exerted on 2 × 2 × 2 cm³ wood specimen of Eucalyptus hybrid. Two relative humidity levels of 93% RH and 27% RH were maintained in dessicators. The per‐cent change in Equilibrium Moisture Content (EMC) was measured. It was found that the initial percent change of EMC was 2.62 times higher in low moisture content specimens when compared to the higher moisture content specimens. The EMC was found to decrease on applying compressive stress irrespective of the stress level. An explanation for this effect in terms of re-alignment of hydrogen bonds is presented in this paper. Received 8 December 1997     

Real-time measurement of vibrational properties and fine structural properties of wood at high temperature

Vibrational properties and fine structural properties of wood were measured at high temperatures. Sitka spruce (Picea sitchensis Carr.) and Shioji (Japanese ash, Fraxinus spaethiana Lingelsh.) were used as specimens. The specimens, the system to support them, a magnetic driver, and a deflection sensor were in an electric drying oven, where vibration tests were conducted. The heating temperatures ranged from room temperature to 200 °C in 25 °C increments in both heating and cooling processes. X-ray diffractometry was carried out using positive sensitive proportional counter (PSPC) at room temperature to 200 °C in 20 °C increments in both heating and cooling processes. Received 13 December 1999     

Adsorption of trivalent chromium from dilute solution by conifer leaves

Summary  Chromium(III), Cr(III) adsorption capacities of the leaves of 34 conifer species were examined. Among these, Ginkgo biloba, Taxus cuspidata, Cephalotaxus harringtonia var. nana, and Taxodiaceae and Cupressaceae spp. showed large capacities to adsorb Cr(III). The adsorption capacities of conifer leaves for Cr(III) (3.12–5.09 mg Cr g⁻¹ adsorbent) compared favorably with those of commercial activated carbons (1.23–2.75 mg g⁻¹). Factors affecting Cr(III) adsorption were studied using G. biloba leaves. The factors included solution pH, contact time, temperature, and the initial concentration of Cr(III). The amount of Cr(III) adsorbed on the adsorbent increased steadily with increasing pH in a pH range from 2 to 5, with increasing contact time, and with increasing temperature ranging 20 to 40 °C. The Cr(III) adsorption was also affected by the initial concentration of Cr(III) in the solution.  A linear relationship was observed between the amount of Cr(III) adsorbed and the equilibrium concentration of Cr(III) in the solution when graphed logarithmically. The maximum capacity of G. biloba leaves was 27.5 mg Cr g⁻¹ adsorbent by column experiments. Received 13 January 1998     

Working mechanism of adsorbed water on the vibrational properties of wood impregnated with extractives of pernambuco (Guilandina echinata Spreng.)

To clarify the lowering mechanism of loss tangen (tan) of sitka spruce (Picea sitchensis Carr.) wood impregnated with extractives of pernambuco (Guilandina echinata Spreng. synCaesalpinia echinata Lam.), we examined the vibrational properties of the impregnated wood in relation to the adsorbed water. The results obtained were as follows: (1) The equilibrium moisture content (EMC) of impregnated sitka spruce decreased to some extent compared with untreated wood. (2) Frequency dependencies of tan a about 400–8000Hz showed that impregnated wood has much lower tan than untreated wood at around 9% mois ture content (MC), except for the high-frequency region. At high relative humidity, impregnated wood has a minimum tan (at around 4000Hz); and at other frequency ranges the tan of impregnated wood did not differ considerably from that of untreated wood. (3) The apparent activation energy of the mechanical relaxation process (E) concerned with adsorbed water molecules was higher for impregnated specimens than for untreated ones at moderately high relative humidity, whereas at high relative humidity the difference was not observed. Based on these results, it is thought that the tan of impregnated wood decreased at low rela tive humidity because of the formation of direct hydrogen bonds between impregnated extractives and wood components. However, when the specimen is at higher relativePart of this work was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998 humidity, the formation of direct hydrogen bonds are disturbed by the existence of a large number of water molecules, and some extractives act as a plasticizer.     

On the loss factor of wood during radio frequency heating

 The radial direction loss factor of full-size western hemlock sapwood and heartwood, as well as western red cedar heartwood timbers was measured using the direct calorimetric method with a laboratory-scale radio frequency/vacuum dryer at the frequency of 13.56 MHz, moisture content range between 10 and 80%, temperature range between 25 and 55 °C, and root mean square (rms) electrode voltages of 0.8 and 1.1 kV, respectively. The results indicated that the moisture content, temperature, electric field strength and wood type significantly affected the loss factor. Empirical regression equations were derived based on the experimental data that made possible the calculation of the loss factor and power density within wood during RF heating. Received 18 January 1997     

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     

Interaction between glycerin and wood at various temperatures from stress relaxation approach

In order to understand the reason why glycerin pre-treatment can accelerate the deformation fixation of compressed wood, the interaction between glycerin and wood at various temperatures was investigated in this study from stress relaxation approach. The compression stress relaxation curves of poplar (Populus cathayana Rehd.) samples impregnated with glycerin were measured at temperatures ranging from 25 to 180°C, together with the curves of oven-dry wood at temperatures between 100 and 180°C for comparison. The activation energy was calculated according to the Eyring’s absolute rate reaction theory. The results showed that temperature had very obvious effect on stress relaxation for both glycerin-treated wood (GTW) and oven-dry wood. The stress released very fast at higher temperatures. Glycerin showed an accelerating effect on stress relaxation. At temperatures exceeding 120°C, a complete relaxation of the stress could be expected. While for untreated wood, it cannot be reached until 160°C. By calculating the apparent activation energy (ΔE) of GTW at different temperatures, it is clear that two mechanisms are responsible for different temperature ranges. From 40 to 100°C, ΔE is only 8.24 kJ/mol, which corresponds to the hydrogen bonds formed between wood and glycerin molecules; from 120 to 180°C, ΔE reached 81.38 kJ/mol, which corresponds to the degradation of hemicelluloses or lignin, and during this process, new cross-linking would happen.     

Diurnal behaviour of <Emphasis Type="Italic">Cephalcia lariciphila</Emphasis> (Hymenoptera: Pamphiliidae): relation to climatic factors and significance for monitoring

Adults of Cephalcia lariciphila emerge and start their activity at Vetrny Jenikov village (Czech Republic) during mid-April. First specimens were collected from Malaise traps at the same time as from emergence traps. Last specimens flew at the beginning of May or even the beginning of June. Adult occurrence typically lasted about 20 (–30) days. One Malaise trap and five yellow sticky boards were placed on three plots, and sawflies were collected at 1 hour intervals in two two-day periods. The variables with the best explanatory power for activity of imagos were temperature in interaction with humidity. Sawflies were most active at 16°C with 20% air humidity and numbers caught decreased steeply up to 0°C and 80% air humidity. The daily flight activity began at 10 a.m. and ended after 5 p.m. Both methods, the Malaise traps and the yellow sticky boards, should be used in forest practices from the middle of April.     

Green color protection of bamboo culms using one-step alkali pretreatment-free process

This study evaluated the protection effectiveness of alcohol-borne reagents for the green color of ma bamboo (Dendrocalamus latiflorus Munro) and moso bamboo (Phyllostachys pubescens Mazel). The results show that the types and concentrations of alcohol-borne reagents, the kinds of solvent, and the conditions of treatment greatly affected the green color of these two bamboo species. Without alkali pretreatment, an excellent green color protection (a* = −14.5) was obtained when the ma bamboo culms were treated with 0.5% methanol-borne copper chloride (CuCl₂) at 60°C for 30 min. Similar results were also obtained when ma bamboo culms were treated with 0.5% methanol-borne copper nitrate [Cu(NO₃)₂] at 60°C for 2 h (a* = −13.5). For moso bamboo, an attractive green color in the bamboo culms was achieved by treating the specimens with 1% methanol-borne copper acetate [Cu(CH₃COO)₂] at 60°C for 30 min. The a* value of treated specimens was −13.3. In addition, results demonstrated that ultrasonic treatment was more effective on green color protection than conventional water bath treatment. When moso bamboo was treated with 1% copper acetate at 60°C in an ultrasonic bath for only 15 min, a remarkable green color with an a* value of −13.6 was obtained on the bamboo epidermis.     

Relaxation mechanism of residual stress inside logs by heat treatment: choosing the heating time and temperature

 Some methods to reduce residual stress inside logs have been reported, although the conditions for stress relaxation are not yet clarified. Our study using precise experiments revealed that residual stress relaxation occurs only when both heat and moisture exist inside the logs. We then determined the heating time and temperature required to relax the residual stress inside the logs. Short air-drying treatments did not relax residual stress even though free water in the logs was greatly reduced. The residual stress of the 33-h 80°C-heated bolts was relaxed, whereas that of the 48-h 70°C-heated bolts was not. As for the influence of treatment time, bolts heated at 100°C were relaxed after 18 h of treatment. The 13-h heated bolts did not show any relaxation. Therefore, residual stress relaxation occurred rapidly owing to the thermomechanical change of the individual wood components comprising the cell wall. The moisture content inside all the bolts was much higher than the fiber saturation point. This is because relaxation occurs only when the heating temperature is maintained above 80°C for a particular duration of treatment. Received: December 12, 2001 / Accepted: February 18, 2002 Present address: Institute for Structural and Engineering Materials, National Institute of Advanced Industrial Sciences and Technology, Independent Administrative Institution, Nagoya 463-8560, Japan Tel. +81-52-736-7320; Fax +81-52-736-7419 e-mail: m.nogi@aist.go.jp Part of this report was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000 Correspondence to:M. Nogi     

Variation of stress wave velocity with MC and temperature

 The effect of moisture content (MC) and temperature on the stress wave velocity and signal frequency spectrum through sapwood has been investigated. It was discovered that in 2.5 m long green boards only low frequencies were present in the transmitted signal, while for boards less than 500 mm long, the much higher resonance frequency of the transducer was dominant. For green boards between 0.5 and 2.5 m both low and high frequency components were present. The frequency spectrum was monitored for a 540 mm long board over a range of moisture contents and temperatures. When the MC was below 30% the transmitted signal waveform consisted almost entirely of the transducer resonance frequency, while at higher moisture contents, low frequency components predominated. The frequency spectrum of the transmitted signal was little affected by temperature, but it was affected by the type of transducers used. The effect of temperature and moisture content on stress wave velocity was studied and is displayed in the form of a three dimensional graph. Received 3 May 1999     

Dynamic viscoelastic properties of wood acetylated with acetic anhydride solution of glucose pentaacetate

 Spruce wood specimens were acetylated with acetic anhydride (AA) solutions of glucose pentaacetate (GPA), and their viscoelastic properties along the radial direction were compared to those of the untreated and the normally acetylated specimens at various relative humidities and temperatures. Higher concentrations of the GPA/AA solution resulted in more swelling of wood when GPA was introducted into the wood cell wall. At room temperature the dynamic Young's modulus (E′) of the acetylated wood was enhanced by 10% with the introduction of GPA, whereas its mechanical loss tangent (tan δ) remained almost unchanged. These changes were interpreted to be an antiplasticizing effect of the bulky GPA molecules in the wood cell wall. On heating in the absence of moisture, the GPA-acetylated wood exhibited a marked drop in E′ and a clear tan δ peak above 150°C, whereas the E′ and tan δ of the untreated wood were relatively stable up to 200°C. The tan δ peak of the GPA-acetylated wood shifted to lower temperatures with increasing GPA content, and there was no tan δ peak due to the melting of GPA itself. Thus the marked thermal softening of the GPA-acetylated wood was attributed to the softening of wood components plasticized with GPA. Received: March 29, 2002 / Accepted: May 21, 2002 Correspondence to:E. Obataya     

Effect of grain angle on shear strength of glued end grain to flat grain joints of defect-free softwood timber

To evaluate the effect of grain orientation on the adhesive bond strength, three-layered Norway spruce wood specimens were tested in shear. The two axial-oriented outer layers were jointed with the middle layer using three typical glues for load bearing constructions, i.e. one-component polyurethane (PUR), melamine–urea–formaldehyde (MUF) and phenol–resorcinol–formaldehyde (PRF). The grain orientation of the middle layers was varied from 0° (parallel to grain of the surface layer) to 90° (perpendicular to grain of the surface layer) in incremental steps of 10°. Samples with middle layers oriented parallel to the outer layers showed shear values in the range of solid spruce wood. Decreased shear strength values were expected for increased grain angles of the middle layer. However, no explicit tendency was observed for the shear strength in dependence of the grain direction. In general, MUF-bonded samples showed slightly higher shear strength values compared with PUR- and PRF-bonded specimens.     

Dynamic viscoelastic behavior of wood under drying conditions

In this study heartwood from a Chinese fir [Cunninghamia lanceolata (Lamb.) Hook] plantation was treated using a high-temperature drying (HTD) method at 115°C, a low-temperature drying (LTD) method at 65°C, and freeze vacuum drying (FVD), respectively. The dynamic viscoelastic properties of dried wood specimens were investigated. The measurements were carried out at a temperature range of −120 to 250°C at four different frequencies (1, 2, 5, and 10 Hz) using dynamic mechanical analysis (DMA). We have drawn the following conclusions: 1) the storage modulus E′ and loss modulus E″ are the highest for HTD wood and the lowest for FVD wood; 2) three relaxation processes were detected in HTD and LTD wood, attributed to the micro-Brownian motion of cell wall polymers in the non-crystalline region, the oscillations of the torso of cell wall polymers, and the motions of the methyl groups of cell wall polymers in the non-crystalline region in a decreasing order of temperatures at which they occurred; and 3) in FVD wood, four relaxation processes were observed. A newly added relaxation is attributed to the micro-Brownian motions of lignin molecules. This study suggests that both the HTD and the LTD methods restrict the micro-Brownian motion of lignin molecules somewhat by the cross-linking of chains due to their heating history. __________ Translated from Journal of Beijing Forestry University, 2008, 30(3): 96–100 [译自: 北京林业大学学报]     

Spectrochemical characterization by FT-Raman spectroscopy of wood heat-treated at low temperatures: Japanese larch and beech

Test samples of Japanese larch (Larix leptolepis) heartwood and Japanese beech (Fagus crenata) sapwood were heated for 22 h at constant temperatures (50°–180°C) under three water content conditions. Raman spectra of the samples were recorded before and after the heat treatments, and spectral changes in the range from 1000 cm⁻¹ to 1800 cm⁻¹ were evaluated using the difference spectrum method. For both wood species, the Raman band intensity at 1655–1660 cm⁻¹ due mainly to the C=C and C=O groups in lignin clearly decreased with increasing heat-treatment temperature (HTT). The spectral change was thought to reflect the progress of condensation reactions of lignin molecules during the heat treatment. Moreover, the decrease in band intensity was considerably facilitated by the presence of water in the cell wall, suggesting that the condensation is closely related to the softening of lignin. From the spectral changes in the wavenumber region of 1200–1500 cm⁻¹, it was considered that wood constituents are partially decomposed at the higher HTT. Part of this article was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, March 2003     

Moisture sorption and swelling of Norway spruce [Picea abies (L.) Karst.] impregnated with linseed oil

Abstract

The moisture sorption and swelling of spruce specimens impregnated with linseed oil and unimpregnated controls were studied in two sorption experiments: from 0 to 55% relative humidity (RH) and from 55% RH to water saturation. Sorption isotherms were also determined using a sorption balance. The impregnated specimens had lower rates of both moisture sorption and swelling than the unimpregnated controls; however, there was no significant difference in final moisture contents. In addition, the linseed oil impregnation did not improve the dimensional stability of the wood; in most cases the specimens impregnated with linseed oil swelled more than the unimpregnated controls. For the impregnated specimens, reductions in swelling rates were in most cases seen without corresponding reductions in final swelling. The moisture sorption rate was reduced for the impregnated specimens but there were generally no reductions in equilibrium moisture content.     

Experimental determination of the convective heat and mass transfer coefficients for wood drying

The knowledge of the convective heat and mass transfer coefficients is required for the characterization of the boundary conditions of the heat and mass transfer equations of a wood drying model based on water potential. A new experimental method for the determination of the convective mass transfer coefficient is presented. This method is based on the measurement of the moisture content, and indirectly the water potential, at the surface of a wood specimen at different drying times. Drying experiments were performed on red pine (Pinus resinosa Ait.) sapwood from nearly saturated to dry conditions at 56 °C, 52% relative humidity and air velocities of 1.0, 2.5 and 5.0 m s⁻¹. The results show that the convective mass transfer coefficient is constant until the wood surface moisture content reaches about 80% and then decreases more or less gradually as the moisture content decreases further. The convective mass transfer coefficient increases with air velocity. A regression analysis shows that there is no significant improvement in considering the water potential gradient near the wood surface when the difference in water potential between the surface and the surrounding air (ψ_s − ψ_∞) is used to determine the convective mass flux at the surface. Also, ψ_s − ψ_∞ is more appropriate than the water vapour pressure difference (pv_s − pv_∞) as the responsible driving force of the moisture flux leaving the wood surface. The convective heat transfer coefficient was determined during the same experiments. A plateau is observed at high values of moisture content corresponding to the constant drying rate period. Received 27 February 1998     

Shrinkage-related degrade and its association with some physical properties in Eucalyptus regnans F. Muell

Summary Assessments of internal checking and the physical properties of 124 trees of Eucalyptus regnans F. Muell. have shown that for material dried under relatively mild predryer conditions (30 °C, 65% RH) internal checking was highly positively correlated with each of collapse, moisture content and normal shrinkage, and weakly negatively correlated with total external shrinkage. Collapse alone explained 47% of the variation in internal checking. Incidence of internal checking in sample boards could be estimated with moderate success by each of the following properties measured on board ends: collapse, the number of internal checks and initial moisture content. Material with high mean basic density above 530 kg/m³ was associated with low levels of internal checking and collapse. However, the maximum naturally occurring density of E. regnans was not high enough to obviate collapse and internal checking. It was observed that growth rings in 100 × 50 mm backsawn boards in which the earlywood air-dry density was below 450 kg/m³ showed internal checking. The size and number of internal checks increased with a decrease in earlywood density. It was shown that drying E. regnans below temperatures of 24–30 °C does not eliminate collapse, thus raising doubt about the validity of a temperature threshold concept in that range. Received 17 September 1997