Durability of isocyanate resin adhesives for wood V: changes of color and chemical structure in photodegradation

The effect of ultraviolet (UV) light irradiation on the color and chemical structure of water-cured polymeric diphenylmethane diisocyanate (PMDI) was investigated using a UV long-life fade meter. Control treatment was performed without UV light irradiation using a thermohygrostat for comparison. Two kinds of resin were used in this study: that to which only water had been added, and resin to which a small amount of polyol and water had been added. In addition, lauan (Shorea spp.) wood was used as a reference. The photodegradation of the resins over a period of up to 300 h was observed using a colorimeter and Fourier transform infrared (FT-IR) spectroscopy. When the resins were treated with UV light, the color difference (ΔE ^* ab) of the resins increased signifi cantly in a short time, and then reached a near-constant value. For lightness, L ^* decreased rapidly for a few hours and then decreased gradually. The color darkened compared with that of the wood used. When treatment was performed without UV light irradiation, ΔE ^* ab and ΔL ^* of the resins showed negligible change. Based on the results of FT-IR analysis, severe degradation such as cleavage of the main chemical bond was hardly observed under UV light irradiation irrespective of the type of resin. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, Japan, and at the 6th International Wood Science Symposium, Bali, Indonesia     

Element content and pH value in American black cherry (<Emphasis Type="Italic">Prunus serotina</Emphasis>) with regard to colour changes during heartwood formation and hot water treatment

Element content and pH value in wood tissues of veneer grade logs of P. serotina Ehrh. were investigated with regard to wood colour variations, measured in the CIEL*a*b* system. The average pH value of heartwood tissue was about pH 4.0 and medium colour parameters of veneer sheets were determined at L* = 73, a* = 9.8, and b* = 23.5. Optical emission spectroscopy (ICP-OES) analyses showed differences in the element contents between two regional forest sites coming from Pennsylvania and West Virginia, USA, respectively. The latter is mainly characterised by higher variations of micro-element content in the transition zone (influencing heartwood formation) and also pH value of wood tissue, which contributes to higher variations in colour response of industrially produced veneer sheets. Investigations under industrial conditions underline the correlation between length and intensity of heat treatment in veneer production and colour development: with increasing duration and temperature of hot water treatment, veneer surfaces become darker and wood colour is intensified (ΔL = 3.6, Δa = 2.1, comparing 12 and 72 h of hot water treatment at 60°C). However, no equalisation of wood colour was achieved by modifying the treatment conditions. Artificial radiation by UV–visible light, quickly and extensively darkens and intensifies wood colour (ΔL = 16, Δa = 3.5, and Δb = 4.0 after 15 h of artificial radiation), but variations in wood colour deriving from different treatment conditions during veneer production, were not reduced.     

Kinetic analysis of color changes in keyaki (Zelkova serrata) and sugi (Cryptomeria japonica) wood during heat treatment

The kinetics of color changes in keyaki (Zelkova serrata Makino) and sugi (Cryptomeria japonica D. Don) wood during heat treatment were examined. The color of wood specimens treated at 90, 120, 150, and 180 °C was measured by an imaging spectrophotometer and expressed using CIELAB color parameters. At any treatment temperature, values for L* and $ \Updelta E_{ab}^{*} $ decreased and increased in both wood species, respectively, with increased treatment time. Changes in a* and b* varied depending on wood species and treatment temperature. The color changes were successfully analyzed using the kinetic approach applying time–temperature superposition method. This approach elucidated and accurately predicted color changes during heat treatment.     

Carbon Isotope Discrimination, Gas Exchange and Stem Growth of Four Euramerican Hybrid Poplars under Different Watering Regimes

Seasonal changes in carbon isotope discrimination (Δ) and gas exchange traits were assessed in four Populus×euramericana clones differing in growth potential. Measurements were made during the second year after establishment in the field under two watering regimes, which were defined by the time-span between flood irrigations, hence resulting in different dry-down cycles: high irrigation (conservative schedule currently applied in the Ebro Valley, Spain) and low irrigation (equivalent to about a one-fourth reduction in water inputs). Net CO₂ assimilation rate (A), stomatal conductance (g_s), intrinsic water-use efficiency (A/g_s) and other related photosynthetic traits (leaf nitrogen concentration, leaf greenness and leaf mass per area) were measured prior to watering, and Δ was analysed in water-soluble leaf extracts (Δ_s) and bulk leaves (Δ_l). Stem growth was monitored over 3 years starting at the year of establishment (1998). Data were subjected to a repeated measures ANOVA over time for a randomised block split-plot design across watering regimes. Significant differences between watering regimes were detected using a long-term estimate of photosynthetic performance such as Δ_l, in agreement with changes in soil water status and evapotranspirative demand. However, the lack of significant genotype×watering regime interactions for gas exchange traits and Δ_s suggested that water shortage imposed by low irrigation was not sufficient to reveal physiological adaptations to drought. In this regard, the reduction in water inputs brought about by low irrigation did not reduce tree growth for any of the clones, suggesting that the current irrigation scheme employed in the region is superfluous to the water consumption needs of poplars. Genotypic variation was detected in gas exchange traits, Δ_s, Δ_l and stem growth under both watering treatments. Significant correlations with stem volume for Δ_s (r = −0.60, p<0.05) and A (r = + 0.61, p<0.05) suggested that growth was improved by higher water-use efficiency (the ratio of carbon fixed to water lost, as inferred by Δ_s) due to variation in A rather than in g_s. This observation corroborated the expectation derived from current theories that a lower Δ is related to higher stem volume, as a result of changes in net CO₂ assimilation rates.     

Effects of UV light irradiation on colour stability of thermally modified, copper ethanolamine treated and non-modified wood: EPR and DRIFT spectroscopic studies

A series of experiments were carried out to investigate the colour stability of chemically treated and thermally modified wood compared to non-modified wood during long term artificial UV light irradiation. One set of wood samples was vacuum-pressure impregnated with alkaline (pH 9.8) copper (II) ethanolamine aqueous solution, while another set of samples from the same wood block was thermally modified at 210°C and −0.90 bar for 2 h. The treated and modified wood samples along with the non-modified ones were exposed to artificial UV light with the wave length in the region of UVA (315–400 nm) and UVB (280–315 nm) intermittently for 500 h. Colour measurements were carried out throughout the irradiation period at an interval of 100 h according to CIEL*a*b* system, where the results are presented in terms of ΔE, ΔL*, Δa* and Δb* values. Better photo-stability in terms of colour changes was recorded for both treated and modified woods compared to the non-modified one. By means of EPR and DRIFT spectroscopic study it was shown that some degree of colour stability of treated and modified woods, achieved during artificial UV light irradiation, resulted from lignin modifications and monomers of phenolic compounds.     

Discolouration of birch wood: analysis of extractives from discoloured surface of vacuum-dried European white birch (Betula pubescens) board

A discolouration that appeared on the surfaces of a European white birch (Betula pubescens) board during vacuum drying was studied by means of colour measurements (CIEL*a*b*), elemental analysis and the analysis of extractives. The discoloured surface layer of the dried board contained substantially more methanol-soluble extractives than did the light-coloured part (50.7 mg g⁻¹ vs. 26.7 mg g⁻¹ dry wood), and the colour difference (ΔE* _ab 20.0) between the two extracts was notable. Characterization by means of GC and ¹³C NMR spectroscopy showed that the extracts contain sugars (mainly glucose and fructose), low-molecular-weight phenolic compounds, proanthocyanidins, Brauns’ lignin and fatty acid esters. Concentrations of sugars, low-molecular-weight phenols, proanthocyanidins and Brauns’ lignin were higher in the discoloured surface layer than in the light-coloured part. The yellowness of the surface layer was associated with the accumulation of low-molecular-weight phenolic extractives, and the redness with Brauns’ lignin and possibly proanthocyanidins.     

Heat-induced colour changes of pine (Pinus pinaster) and eucalypt (Eucalyptus globulus) wood

Heat treatment of Pinus pinaster and Eucalyptus globulus wood was carried out by hot air in an oven for 2–24 h at 170–200°C and by steam in an autoclave for 2–12 h at 190–210°C. The colour parameters L*, a* and b* were determined by the CIELAB method on radial, tangential and transverse sections of untreated and treated wood, and their variation with regard to the treatment (ΔL*, Δa* and Δb*) were calculated in percent. For untreated eucalypt wood, lightness (L*) varied between 54.1 and 63.8% with a* between 7.4 and 8.5, and b* between 15.7 and 19.9. For untreated pine wood, L* varied between 67.3 and 76.1%, a* between 6.9 and 7.6 and b* between 16.3 and 24.1. Oven heat-treated wood became darker (ΔL* about 50% for 4% mass loss), and this was more for eucalypt wood under the same treatment conditions. In general, the contribution of red (a*) and yellow (b*) colour decreased with heat treatment. The transverse section of the two species darkened less for both the treatments with small differences between radial and tangential sections. Lightness decrease was related to chemical changes; with good correlations with glucose (R ² = 0.96), hemicelluloses (R ² = 0.92) and lignin (R ² = 0.86). As regards colour, the heat treatments showed an interesting potential to improve the wood quality for solid timber products from pine and eucalypt.     

Inventory and eddy covariance-based estimates of annual carbon sequestration in a Sitka spruce (<Emphasis Type="Italic">Picea sitchensis</Emphasis> (Bong.) Carr.) forest ecosystem

A comparison was made of annual net ecosystem productivity (NEP) of a closed canopy Sitka spruce forest over 2 years, using either eddy covariance or inventory techniques. Estimates for annual net uptake of carbon (C) by the forest varied between 7.30 and 11.44 t C ha⁻¹ year⁻¹ using ecological inventory (NEP_eco) measures and 7.69–9.44 t C ha⁻¹ year⁻¹ using eddy covariance-based NEP (-NEE) assessments. These differences were not significant due to uncertainties and errors associated with estimates of biomass increment (15–21%) and heterotrophic respiration (12–19%). Carbon-stock change inventory (NEP_ΔC ) values were significantly higher (27–32%), when compared to both NEP_eco- and -NEE-based estimates. Additional analyses of the data obtained from this study, together with published data, suggest that there was a systematic overestimation of NEP_ΔC -based assessments due to unaccounted decomposition processes and uncertainties in the estimation of soil-C stock changes. In contrast, there was no systematic difference between NEP_eco and eddy covariance assessments across a wide range of forest types and geographical locations.     

Changes in the physical and chemical properties of six Japanese softwoods caused by lengthy smoke-heating treatment

The effects of prolonged smoke-heating treatments on wood quality were investigated. Six Japanese softwoods were smoke-heated for 100 and 200h at a temperature of 75° ± 5°C, which was recorded inside the log. After smoke heating, wood quality, including moisture content, amounts of chemical components, relative degree of crystallinity (RDC) of cellulose, and sapwood color were examined. Moisture content decreased as a result of smoke heating, especially in sapwood, leading to a uniform distribution of moisture content within a log. Almost no difference was found in the amounts of chemical components between the control woods and the woods that were smoke-heated for 100h. However, in the wood that was smoke-heated for 200h, the amounts of holocellulose decreased, suggesting that thermal deterioration and/or degradation of hemicelluloses had occurred. We assume that the increase in RDC was caused by smoke heating with the crystallization of cellulose and/or thermal degradation of hemicelluloses. Almost no differences were found in sapwood color between the control woods and the woods that were smoke-heated for 100h. In the wood that was smoke-heated for 200h, however, L*decreased, whereas a* and b* increased. As a result, E*ab, showing the total color change, increased, resulting in a deeper color. These results suggest that thermal degradation of hemicelluloses was caused by smoke heating for over 100h. Therefore, smoke heating of softwood logs using a commercial-scale kiln should not exceed 100h.     

Effects of different N sources on growth, nutrient uptake and ionic balance ofLarlix gmelini seedlings

The effect of different sources and levels of N on dry matter production, nutrient uptake and ionic balance ofLarlix gmelini was studied. The results showed that the growth of the plants fertilized with ammonium was not as good as the control treatment. The growth of the plants fertilized with ammonium nitrate did not differ significantly from that in control or nitrate treatment, but was better than that in the ammonium treatment. Total cation concentrations in shoots varied little with N level in the ammonium and ammonium nitrate treatments, while those in the shoot increased with N level in the nitrate treatment. The treatments had little effect on the anion concentrations in the shoot. In the roots, the concentrations of both cations and anions changed little except for SO₄ ²⁻ and Ca²⁺. There existed a higher carboxylate production in the plants fertilized with nitrate. The ratio between the production of carboxylate and the production of organic N Δ(C-A)/ΔN_org was constant with N supply in the plants receiving nitrate, but obviously declined with N supply for ammonium-fed plants. Δ (C-A)/ΔN_org values were intermediate between those of the nitrate and the ammonium-fed plants as for the mixed N source. Foundation item: This paper was supported by “Hundred Scientists” Project of Chinese Academy of Sciences. Biography: CHEN Yong-liang (1969-), male, Ph. Doctor, lecture of Northeast Forestry University, Harbin 150040, Post-doctor in Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, P.R. China. Responsible editor: Song Fuman     

Dielectric properties of silicon dioxide/wood composite

For a better understanding of the binding between silicon dioxide and wood as well as the dielectric properties of silicon dioxide/wood composite, dielectric relaxation was measured for untreated wood [Cunninghamia lanceolata (Lamb.) Hook] and for silicon dioxide/wood composite with different weight percentage gain (WPG). Cole–Cole’s circular arc law, distribution spectrum of relaxation time and relation model were applied to the results of relaxation due to motions of the methylol groups. The results were as follows. The generalized relaxation time and ε _s − ε _∞ decreased with increasing WPG. The distribution spectrum of relaxation time decreased more and more and broadened with increasing WPG. The methylol group in the amorphous region of the wood cell wall participated in hydrolysis reaction and condensation reaction caused by tetraethylorthosilicate (TEOS), and there is a cross-link between silicon dioxide and wood. The value of apparent activation energy (ΔE) increased for silicon dioxide/wood composite, and increased with increasing WPG. Activation enthalpy (ΔH) and activation entropy (ΔS) increased, while activation free energy (ΔG) decreased with increasing WPG. The number of hydroxyl groups cut in dielectric relaxation increased with increasing WPG.     

Investigation on hydrogen abstraction from methyl glucoside by active oxygen species under oxygen delignification conditions III: effects of the origin of active oxygen species

Carbohydrate model compounds methyl β-d-glucopyranoside (MGPβ), methyl α-d-glucopyranoside (MGPα), and methyl β-d-mannopyranoside (MMPβ) and the deuterium compounds of MGPβ labeled at the anomeric or C-2 positions (MGPβ-1D, MGPβ-2D) were reacted with active oxygen species (AOS) generated in situ by reactions between O₂ and a co-treated phenolic lignin model compound, 4-hydroxy-3-methoxybenzyl alcohol (VAlc), under conditions simulating oxygen delignification (0.5 mol/l NaOH, 0.36 mmol/l Fe³⁺, 1.1 MPa O₂, 95°C). MGPβ was degraded more than MGPα but less than MMPβ when the pairs MGPβ/MGPα and MGPβ/MMPβ, respectively, were treated, which indicates that the configurational differences at the anomeric and C-2 positions influence the reactivity of AOS toward these compounds. When the pairs MGPβ/MGPβ-1D and MGPβ/MGPβ-2D were treated, no clear kinetic isotope effects were observed in either case. These results contrasted with those obtained when another phenolic compound, 2,4,6-trimethylphenol (TMPh), was used as the AOS generator instead of VAlc under exactly the same conditions. Clear kinetic isotope effects were observed when using TMPh. Because it is not easily accepted that the anomeric and C-2 hydrogen abstractions are minor reaction modes only for AOS generated in the VAlc system, it is suspected that the AOS do not show any clear kinetic isotope effect even though the AOS abstract an objective hydrogen.     

The effect of axial strain on crystalline cellulose in Norway spruce

The effect of strain on dry, clear Norway spruce (Picea abies [L.] Karst.) wood was studied by tensile testing along the cell axis and by in situ X-ray diffraction measurements. The mean microfibril angle (MFA) was initially 3–12 degrees and did not decrease due to strain. Based on the positions of the reflections 200 and 004 of crystalline cellulose, cellulose chains elongated and the distance between the hydrogen bonded sheets of chains decreased due to the strain. The elongation of the unit cell parallel to the cellulose chains was twice as high in juvenile wood as in mature wood. The (X-ray) Poisson ratio ν _ca for crystalline cellulose in Norway spruce was calculated from the deformation of the unit cell. The average ν _ca of earlywood was 0.28 ± 0.10 in juvenile wood and 0.38 ± 0.23 in mature wood. In latewood, the average ν _ca was 0.48 ± 0.10 in juvenile wood and 0.82 ± 0.11 in mature wood. The average ν _ca values were not directly correlated to the crystallite dimensions or to the mean MFA in juvenile and mature earlywood and latewood. The results show that the amorphous matrix has a definite effect on the deformation of cellulose crystallites.     

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.     

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

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

Is the ranking of poplar genotypes for leaf carbon isotope discrimination stable across sites and years in two different full-sib families?

Introduction   

Because of its vigorous growth, poplar can play an important role for sustainable production of woody biomass to cover renewable energy needs. Hence, the selection of suitable genotypes has to be based on relevant traits, among which intrinsic water use efficiency (W _i, estimated through leaf carbon isotope discrimination, Δ) may be a key trait. Besides a large genetic variation in Δ among the frequently planted poplar hybrids, the use of Δ in deployment or breeding programmes requires insights in the robustness of the genotype ranking for Δ across environments and years.     

Allomorphs of native crystalline cellulose I evaluated by two equatoriald-spacings

The aim of this study was to develop a facile method for categorizing native celluloses as the algal-bacterial type or the cotton-ramie type and for estimating the I_α/I_β (triclinic/monoclinic) ratio of the cellulose samples. We investigated various native celluloses by X-ray diffractometry; and discriminant analysis was carried out using two equatoriald-spacings: 0.59–0.62 nm (d ₁) and 0.52–0.55 nm (d ₂). All of the samples were classified into the two groups without error. The function used to discriminate between the two groups is represented as:Z=1693d₁ — 902d ₂ — 549, whereZ>0 indicates the algal-bacterial (I_α-rich) type andZ<0 indicates the cotton-ramie (I_β-dominant) type. Another X-ray diffraction study of hydrothermally treatedCladophora cellulose revealed the relation between thed-spacings (d ₁,d ₂) and the I_α/I_β ratio. A calibrating equation by which the I_α/I_β ratio was estimated from the two parameters,d ₁ andd ₂, was then prepared. In the case of relatively highly crystalline native celluloses, it was found that the I_α/I_β ratio is easily determined by applying the two parameters in the equation.     

Coloring characteristics of in situ lignin during heat treatment

To investigate the effects of lignin on the discoloration of Black locust (Robinia pseudoacacia) wood during heat treatment, chromatic indexes of the extractive-free wood samples are examined at different moisture contents (MC) under oxygen and nitrogen environment, respectively. The organic acids are produced during heat treatment, resulting in pH decrease in the samples. Components absorbing visible light are formed during heat treatment, and oxygen and moisture contents have obvious effects on the decrease in L*, increase in a* value, yellowness (b*) and total color difference (ΔE) of the samples. It is found that the β-5, C _α C _β unsaturated bond, the conjugated carbonyl group, quinones structures, α, β-unsaturated ketone and α-C?=?O in lignin increased after heat treatment. The formation of condensation products, the low-molecular-weight phenolic substances and the oxidation products in lignin result in the increment of the light absorption within the entire visible region.     

New diagrams to evaluate soil pore radius distribution and saturated hydraulic conductivity of forest soil

Based on the widely used soil pore classification systems, soil pore ratios α, β and γ were derived. α, β, and γ represent ratios of the fine capillary porosity, coarse capillary porosity, and non-capillary porosity to the effective porosity, respectively. The parametersψ _m and σ of the soil water retention model developed by Kosugi were related to these pore ratios, and a simple method was suggested to estimateψ _m and σ from measured soil pore ratios. By analyzing the observed retention data sets of forest soils, it was shown that the soil pore ratios are effectively used to evaluate the soil pore radius distribution. A coordinate system with log(−ψ _m ) on the abscissa and σ on the ordinate, which represents the constant α, β, and γ lines, was developed as a new diagram to evaluate the soil pore radius distribution in connection with the soil water retention characteristic. Then, the saturated hydraulic conductivityK _s of forest soils was correlated with the parametersψ _m and σ, and with the ratios α, β, and γ using the coordinate system and the triangle diagram. Results showed thatK _s is higher for the soil with a greater median and with a greater width of the pore radius distribution.K _s increases as the non-capillary pore ratio γ becomes greater and the coarse capillary pore ratio β becomes smaller. Functional relationships betweenK _s and the water retention parameters, and betweenK _s and the soil pore ratios were derived based on Mualem's model. The title is tentative translation from the original Japanese title by the author of this paper.     

Ecophysiology and Survival of Acer pseudoplatanus L., Castanea sativa Miller. and Quercus frainetto Ten. Seedlings on a Reforestation Site in Northern Greece

Seedlings of three tree species (Acer pseudoplatanus L., Castanea sativa Miller. and Quercus frainetto Ten.) were planted on a field site in Northern Greece to investigate factors connected to planting failures. On several dates, for the first two growing seasons after planting (1997 and 1998), leaf water potential, chlorophyll fluorescence, gas exchange variables and seedling survival were determined. Q. frainetto seedlings exhibited the lowest values of leaf water potential (Ψ) for most of the season in both studied years. Seedlings of all species showed large reductions in Ψ the mid-summer in both years, with particularly low values in 1998. In both years, a sharp reduction in Ψ was observed at the beginning of July when all three species exhibited their lowest net CO₂ assimilation (A) rate by the end of July. In 1997, A recovered after the July depression to values even higher than those recorded in June. However, in 1998, only Q. frainetto and to a lesser degree C. sativa recovered from a similar July depression in physiological values. Species reached their highest A rates by the end of August in 1997 and in June during 1998. In general, stomatal conductance and transpiration rates paralleled the A patterns. In 1997, the seasonal course of effective quantum yield (ΔF/F_m), for all plant species followed a rise-and-fall pattern with a peak at the beginning of July. In 1998, ΔF/F_m values were relatively high in June, showed a deep depression during July and while Q. frainetto and C. sativa recovered afterwards, A. pseudoplatanus continued to exhibit very low values. This study showed that differences in mortality between species were due to differences in tolerance to water stress and the superiority of Q. frainetto was probably related to the fact that it was the only species native and adapted to the planting site