难溶无机硼酸盐的制备及其硼流失性能

通过复分解反应,制备出难溶于水的无机硼酸盐,并测定其有效成分的质量分数和难溶硼酸盐处理材的硼流失率。结果表明:与硼砂处理材相比,难溶硼酸盐处理材的硼流失率均有不同程度的降低;水溶型制剂处理材的硼流失率在83.2%～96.8%之间,有机溶剂型制剂处理材中,硼的流失率低至2.7%。     

A new boron impregnation technique of wood by vapor boron of boric acid to reduce leaching boron from wood

This study was designed to reveal impregnation ability and to enhance leaching resistance of boron from borate-treated wood. Vapor boron treatment was applied in compressed and uncompressed states at high temperatures such as 180 and 200°C for 6, 8 and 15 min. Following ten-cycle leaching periods, amounts of boron leached from vapor boron treated wood was measured by ion chromatography. According to the results, boric acid can be vaporized under heat and can be impregnated into wood. Success of the technique can be increased by increasing vapor pressure in a closed chamber. Leachability results proved the boron vaporization along with water vapor at various ratios depends on the process variables. These results have importance on dry wood treatment under heat by boron vapor with a little water presence which does not necessitate a further drying process.     

Low molecular weight silicic acid – inorganic compound complex as wood preservative

A new wood preservative containing low molecular weight and low-toxicity silicic acid (LWSA) was investigated. To prevent environmental pollution with the wood preservative, a silicic acid monomer aqueous solution (SAMS) or colloidal silicic acid solution (CSAS) was combined with various metal compounds or boric acid. Agents where SAMS or CSAS was combined with boric acid gave good protection against decay caused by the brown-rot fungus Fomitopsis palustris, the treated wood (Cryptomera japonica D. Don) specimens after the leaching test maintained a high resistance to decay. The leaching and decay tests revealed high quantities of chemicals leaching from wood treated with SAMS-metal agents. However, when wood was treated with SAMS-boric acid, there was little leaching of agent in either test. The mechanism of resistance of wood, which was treated with boric acid mixed with CSAS or SAMS, to the brown-rot fungus F. palustris were investigated. When the concentration of boric acid was high, mycelial growth was inhibited completely and no protein production was detected. When the amount of boric acid was low, the xylanase, mannase and cellulase activities were lower than with control wood powder. When powdery boric acid was combined with CSAS, it was considered that the treated woods have higher anti-weather properties than when boric acid-methanol solution was mixed with CSAS. The agent-preparation method adopted should be considered carefully after taking the treatment process and the intended use of the preservative-treated wood into account. Received 26 September 2000 This study was supported by a Grant-in-Aid (09460079) for Scientific Research from the Ministry of Education, Science, and Culture of Japan.     

Enhancement of the biological resistance of wood by phenylboronic acid treatment

Phenylboronic acid (PBA) was tested in terms of boron leachability from treated wood. In addition, the fungal and termiticidal efficacy of PBA-impregnated sugi (Cryptomeria japonica D. Don) wood was tested against the decay fungi Coriolus versicolor (L. ex Fr.) Quel. and Tyromyces palustris (Berk. et Curt) Murr., representing white-rot and brown-rot fungi, respectively, and the Formosan subterranean termite Coptotermes formosanus Shiraki. Ion chromatography analysis of hot water extracts of treated wood before and after leaching indicated that PBA is considerably resistant to water leaching, and saturation of the treatment solution increased the fixation ratio of boron in wood, whereas boric acid could not remain in wood impregnated even with the saturated solution. Decay test results revealed the excellent bioactive performance of PBA. Wood treated with 0.34% PBA solution was found resistant to both decay fungi, even after running-water leaching for 10 days and treatment with 1.00% PBA completely inactivated the Formosan subterranean termite for the leached specimens. Weight gain levels were 0.18% w/w (0.46kg/m³) and 0.99% w/w (2.49kg/m³) for these concentration levels, respectively, after being leached by running water. Contrary to the general belief that boron is a slow-acting toxicant against termites and unable to prevent mass loss of treated wood, PBA acted rapidly, and the mass loss caused by termites was low.This study was presented in part at the 47th annual meeting of the Japan Wood Research Society, Kochi, April, 1997     

糠醇邻苯二甲酸单酯的合成

以糠醇和邻苯二甲酸酐为原料，通过控制酯化反应条件，制备了糠醇邻苯二甲酸单酯。有关该化合物的合成及相关数据未见文献报道。     

Effects of polyvinyl alcohol on leachability and efficacy of boron wood preservatives against fungal decay and termite attack

In this study, the use of polyvinyl alcohol (PVA) as boron fixative agent was investigated. Two levels of PVA (2.5 and 4%) were evaluated with disodium octaborate tetrahydrate (DOT) at three concentrations (1, 2 and 4% boric acid equivalent (BAE)) using a double vacuum impregnation process on Scots pine sapwood specimens. Leaching was performed according to a laboratory leaching procedure. Boron analysis using atomic absorption spectrometer showed a significant reduction in boron leachability for the samples treated with both concentrations of PVA when compared to the stand-alone boron treatment leading to boron retentions capable of preventing wood biological degradations. Decay resistance of the leached specimens was evaluated using the brown rot fungus Poria placenta. Even if complete protection was not fully achieved, an improvement in decay resistance was observed for the samples treated with DOT in presence of PVA. This leak of efficacy was attributed to a decrease in the biological activity of the complexed boron against fungi. Durability of treated wood against termite attack, evaluated using Reticulitermes santonensis, indicated a significant enhancement for the samples treated in presence of the fixative agent compared to the pure boron treatment.     

Variation in treatability of Scots pine (Pinus sylvestris) by the chemical modification agent furfuryl alcohol dissolved in water

Scots pine (Pinus sylvestris) sapwood was investigated for variation in treatability using the wood modifying agent, furfuryl alcohol (FA) in water. The variation in treatability within trees, between trees and between different stands of Scots pine was studied. Investigated variables that reduced the residual variance significantly were: site location, latitude of site, height of trees, annual ring width, vertical and horizontal position in the tree and method of drying. Linear mixed model statistics were used and tree number was handled as a random variable. The best model reduced the treatability residual variance by 67%. Location was the single factor affecting treatability most. Differences in latitude between locations may be the reason for that. Latitude correlated negatively with the treatability. Within the trees, the treatability of sapwood increased with distance from ground and with distance from heartwood border. A small, but significantly better treatability was found for kiln dried wood (60°C) compared to air dried wood (20°C).     

New cell wall and cell lumen wood polymer composites

Summary Furfuryl alcohol-based (FA) cell wall and methyl methacrylate-based (MMA) combination formulations were used to make wood polymer composites (WPC). Swelling gradients developed during preparation. Properties (density, hardness, water extractables, antiswell efficiency) gradients were observed along samples in 5 of the 7 treating formulations. Two cell wall treatments based on furfuryl alcohol did not show the gradients. The results suggest treating solution separations occurred during impregnation and the resulting nonhomogenious chemical produced the properties gradients. WPC made using the combination formulations based on MMA had properties which fell between cell wall and cell lumen formulations.It is gratefully acknowledged that Mr. Michel Andrew, Student Assistant, carried out the experiment part of this study     

Modeling of simultaneous three-dimensional leaching and chemical reaction of CCA components in unfixed wood exposed to water

The leaching of chromated copper arsenate (CCA) components from unfixed wood immersed in water is modeled in three dimensions using an analytical model of simultaneous diffusion and reaction. Parameters for the model were determined by laboratory leaching experiments with small uncoated wood samples, departing from previous approaches where diffusion coefficients are measured in one dimension at a time. The diffusion coefficients and reaction rate constants of Cr⁶⁺, total Cr, Cu, and As in unfixed CCA-treated red pine (Pinus resinosa Ait.) and southern pine (Pinus sp.) were estimated, assuming first-order reaction rate equations and independent Fickian diffusion for all components. Estimated reaction rate constants and diffusion coefficients were not significantly affected by sample dimensions except for very severe longitudinal leaching from short samples. The predictive ability of the model using diffusion coefficients determined from immersion of small lab samples was evaluated by leaching experiments in a spray booth of southern pine lumber at 21 and 60°C, and red pine pole sections at 21°C. The predictive ability of the model was mixed, but in all cases represents a significant improvement over small-block leaching models which do not account for the diffusive nature of the leaching process.     

Distribution of boron in wood treated with aqueous and methanolic boric acid solutions

The distributions of boron in Japanese cedar (Cryptomeria japonica D. Don) sapwood blocks treated with aqueous or methanolic boric acid [B(OH)₃] solutions were explored through Raman spectroscopy and prompt gamma-ray analysis (PGA). B(OH)₃ was the sole boron species observed in Raman spectra of the wood blocks treated with either solution. Plots of weight gain of the treated wood blocks versus boron concentration in treatment solutions were found to be linear. The results indicated that the methanolic solution makes it possible to impregnate wood with much larger amounts of boron than the aqueous solution. PGA confirmed that B(OH)₃ was highly enriched near the end grains of the treated wood blocks. Raman measurements suggested that boron content in the bulk of the wood block is not as large as expected from the weight gain of the treated wood blocks when an ordinary air-drying method is used. It was concluded that the aqueous solution impregnates the cell walls of wood with boron more easily than the methanolic solution. Part of this report was presented at the 55th (Kyoto, March 2005) and 56th (Akita, August 2006) Annual Meetings of the Japan Wood Research Society. This article follows the previous rapid communication “Analysis of boron in wood treated with boric acid solutions using Doppler broadening method of prompt gamma-rays.” J Wood Sci (2006) 52:279–281     

Ultraviolet resistance and other physical properties of softwood polymer nanocomposites reinforced with ZnO nanoparticles and nanoclay

Wood polymer nanocomposites (WPNCs) based on nano-ZnO and nanoclay were prepared by impregnation of melamine formaldehyde–furfuryl alcohol copolymer, 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU), a cross-linking agent and a renewable polymer obtained as a gum from the plant Moringa oleifera under vacuum condition. Fourier transform infrared spectroscopy (FTIR) and X-ray diffractometry (XRD) studies were employed for the characterization of modified ZnO and WPNCs. The change in crystallinity index (CrI) value of the cellulose in wood and the distribution of ZnO nanoparticles in composites were determined using FTIR and XRD. Scanning electron microscopy and Transmission electron microscopy showed the presence of nanoparticles and nanoclay in the cell lumen or cell wall of wood. An enhanced UV resistance property was shown by the treated wood samples as judged by lower weight loss, carbonyl index, lignin index, cellulose CrI values, and mechanical property loss compared to the untreated wood samples. Wood polymer composites treated with 3 phr each of nanoclay, ZnO, and the plant gum showed an improvement in mechanical properties, flame-retarding properties, thermal stability, and lower water uptake capacity.     

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.     

Development of chemometric models based on near infrared spectroscopy and thermogravimetric analysis for predicting the treatment level of furfurylated Scots pine

The use of furfuryl alcohol (FA) as a wood modification agent has been known for decades. An independent and reliable analytical method to determine the level of furfurylation is not available. This article reports the use of near infrared spectroscopy (NIR) and thermogravimetric analysis (TGA) to make partial least square prediction models for determining the furfurylation level (the percentage of FA polymer formed within the wood structure). A total of 115 individual samples of furfurylated Scots pine (Pinus sylvestris) originating from 115 production batches were used for modelling. As much as 81 samples were randomly selected for the calibration set and 34 samples for the validation set. Both NIR and TGA gave good predictions when validated by a separate test set. The r ² for NIR and TGA are 0.93 and 0.94, respectively, and the root mean square errors of predictions are 1.025 and 0.958, respectively. However, the number of principal components for the NIR and TGA models is two and six, respectively. The NIR method is preferred because only two principal components are used and sampling is fast.     

Polymerisation of added coniferyl alcohol by inherent xylem peroxidases and its effect on fungal decay resistance of Norway spruce

It is known that active peroxidase isozymes exist in mature wood of Norway spruce (Picea abies L. Karst.) and that they remain active for years and are found even in the heartwood (in Scots pine), where all cellular activity has ceased. This peroxidase activity was utilised in the impregnation of wood blocks with a natural monolignol, coniferyl alcohol and hydrogen peroxide. The hypothesis was that the internal wood peroxidases would oxidise the added monolignol and bind it stably into the cell wall matrix, which could hinder fungal decay. Since coniferyl alcohol is not very soluble in water, the impregnation was done under vacuum with an acetone–water solution containing 10% coniferyl alcohol and 0.4 mM H₂O₂ at room temperature (ca. 0.02 g of coniferyl alcohol was added to 1 g of wood). After impregnation, dimers of coniferyl alcohol and free coniferyl alcohol were found in acetone extracts with GC–MS analysis. Penetration of coniferyl alcohol and non-extractable reaction products were studied from the wood blocks with FTIR PAS technique. The wood samples treated were also subjected to a fungal decay test with Coriolus versicolor. This treatment hindered fungal decay in a 60-day experiment and led to a dry weight loss of 8.8% in comparison with 19.9% in the control. The reactions of coniferyl alcohol and H₂O₂ in the presence of peroxidases are discussed as well as the use of monolignols to increase wood decay resistance.     

改善硼类木材防腐剂流失性的方法及建议

硼类木材防腐剂是环保型防腐剂,但其易流失的缺点使其在户外的应用领域受限。通过总结和归纳防腐处理方法、助剂的应用与特殊硼化物的应用,及提高硼类防腐剂抗流失性的研究进展,为硼类防腐剂扩大应用及今后进一步研究和推广方向提出建议。     

Corrosion of metal fasteners embedded in acetylated and untreated wood at different moisture contents

ABSTRACT

Acetylated wood is now commercially available and designed to be used in certain outdoor applications as an alternative to preservative-treated wood. Fastener corrosion can be a concern in preservative treated wood when the wood remains wet for long periods. However, little data on the corrosiveness of acetylated wood exists beyond the product literature. Here we examine the corrosiveness of commercially obtained acetylated wood and compare it against unmodified (untreated) southern pine (Pinus spp.). Corrosion rates of plain carbon steel, hot dip galvanized steel, and stainless steel were calculated gravimetrically after a one year exposed in the wood. Four different moisture conditions were examined: 90% relative humidity (RH), 95% RH, 100% RH, and a fully water saturated condition. When compared to literature data on the corrosion of fasteners in preservative treated wood at 100% RH, the acetylated wood had much lower steel corrosion rates than all preservatives examined; the measured corrosion rates for galvanized steel were lower than all preservatives except chromated copper arsenate. These measured corrosion rates across a range of moisture conditions can be used to inform the selection of appropriate corrosion resistant fasteners when building with acetylated wood.     

Postia placenta decay of acetic anhydride modified wood – Effect of leaching

Abstract

It is well established that acetylation of wood by the use of acetic anhydride is able to impart a significant degree of decay resistance. The aim of this work was to study how a standardized leaching procedure with water (EN 84) affected the degradation of acetic anhydride modified samples by the brown rot fungi Postia placenta compared to no leaching prior to incubation. Three different levels (low, medium, and high) of acetic anhydride modified Southern yellow pine (SYP; Pinus spp.) were tested. The samples were harvested after 4 and 28 weeks. We compared changes in mass loss, wood moisture content, fungal DNA, and gene expression from five genes. If leaching changes the acetylated samples and makes them more susceptible for fungal deterioration, the expected effect would be higher levels of these parameters. Generally, leaching resulted in few differences between leached and nonleached samples at low levels of acetylation, while no changes were found for the highest acetylation level. No differences were found in gene expressions after 28 weeks. The possible protection of acetylated wood against oxidative fungal degradation is suggested to be interpreted in combination with the lowered wood moisture content.     

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.Part of this report was presented at the 53rd Annual Meeting of the Japan Wood Research Society, Fukuoka, April 2003     

Termite resistance of beech wood treated with zinc oxide and zinc borate nanocompounds*

The field of wood protection is currently changing due to the restrictions imposed by the Biocidal Products Regulation. The need for development of new wood protection technologies is therefore growing. In this work, the resistance of European beech (Fagus sylvatica L.) wood impregnated with nano-dispersions of zinc oxide (nano-ZnO) and zinc borate (nano-ZnB) against the termite Reticulitermes grassei Clement was investigated. Three different concentrations (0.5%, 1%, 2%) of the nanocompounds were tested. The effects of water leaching were also investigated. A severe effect in terms of termite workers mortality was induced by both dispersions, even at the lowest concentration. In terms of termite feeding, nano-ZnO dispersions appeared to be more efficient than nano-ZnB as they induced significant improvement at concentrations as low as 0.5%. Nano-ZnB was applied at 1% or higher concentrations in order to impart similar changes. Nano-ZnB dispersions were efficient in terms of termite resistance for a concentration at least 1%. Further increasing concentration to 2% resulted in a respective increase of wood efficacy against termites. For both tested nanocompounds, water leaching did not result in any significant increase of termite feeding.