Effects of alkyl chain length and the mixing of homologues with different alkyl chains on the leaching characteristics of benzalkonium chloride

Benzalkonium chloride (BAC) is the active ingredient of ACQ-1, one of the most widely used wood preservatives in Japan. BAC in ACQ-1 comprises homologues with different alkyl chains: C12 comprises 74%; C14 26%; and C16 < 1%. To clarify the leaching characteristics and the factors affecting the leaching of BAC homologues, wood specimens treated individually with the C12, C14, and C16 homologues were used in a leaching experiment with distilled water (DW) and artificial sea water (SW). The leaching rates of the BAC homologues were accelerated by the SW, and the order of the leaching rate in both DW and SW was C12 > C14 > C16. When the specimens were treated with a mixture of two of the three homologues, the leaching rates of the C14 and C16 homologues from specimens treated with a solution containing C14 and C16 were lower than that from specimens treated with a solution containing the C14 or C16 homologue together with C12. From the adsorption isotherm of the homologues it is assumed that the formation of BAC aggregates on the treated wood is related to their leaching. BACs consisting of mainly C14 and C16 are thought to be suitable for reducing leaching, particularly in marine usage.     

Effect of components of leaching medium on the leaching of benzalkonium chloride from treated wood

Different leaching media composed of watersoluble extracts from Sakhalin fi r, Japanese cedar, and Japanese larch heartwoods and of taxifolin were used to characterize leaching of the C12 and C14 homologues of benzalkonium chloride from treated wood. The leaching medium of Sakhalin fi r extract moderately accelerated the leaching rates of the two homologues. Japanese cedar extract accelerated the leaching of the C12 homologue at a similar rate and that of the C14 homologue at a higher rate. Japanese larch extract remarkably accelerated the leaching rates of both homologues, particularly that of the C14 homologue. Thus, the leaching rate of the C14 homologue was higher than that of the C12 homologue with the Japanese cedar and larch extracts. The media of taxifolin, a major phenolic extractive of Japanese larch, preferentially accelerated the leaching rate of the C14 homologue. The amounts of phenolic compounds in the different leaching media were in the following order: Japanese larch > Japanese cedar > Sakhalin fi r. These results indicate a relationship between the amount of phenolic compounds and the leaching rates of the two homologues.     

Leaching behaviour of benzalkonium chloride homologues in soil and water solutions

Experiments were carried out to determine the leaching mechanism of benzalkonium chloride (BAC) from treated wood in soil. Wood specimens were treated with C12, C14 and C16 BAC homologues and exposed to soil or aqueous solutions containing oxalic acid, sodium oxalate, hydrochloric acid, sodium chloride or sodium humate. The leaching rates of the homologues in soil were close to each other and all higher than in distilled water. The order of the rates in soil (C12 ≈ C14 ≈ C16) was different from that in distilled water (C12 > C14 > C16). The leaching rates of the homologues in the acidic solutions and their salts solution were also higher than in distilled water, and the order of the rates was the same as in distilled water. The aqueous solution of sodium humate also accelerated homologue leaching but resulted in an order of C16 > C14 > C12. The BAC leaching acceleration mechanism by humate was thought to be different from the mechanisms of acids and their salts and plays an important role in the leaching behaviour of BAC in soil.     

Monoethanolamine extraction of copper-preservative-treated wood and reuse of the extract for wood preservation

Remediation of copper-based alkaline copper quat (ACQ) and micronized copper quat (MCQ) wood-preservative-treated weathered southern pine mulch samples by monoethanolamine (Mea) extraction was studied. The potential reuse of Mea extract in ACQ wood preservative application was also evaluated. Continuous column extraction of copper-preservative-treated samples for 32 h, using 12 % Mea removed 66–86 % (between top and bottom of the column) and 65–80 % of Cu, respectively, from ACQ- and MCQ-treated wood. Mea extracts of treated wood could be reused in ACQ-treating solutions that met the American Wood Protection Association standard specifications for ACQ wood preservatives. This was achieved either by mixing the extract with industrial Cu–Mea solution at 1:4 ratio or by adding cupric acetate salt directly into the Mea extract. ACQ-treating solutions reformulated using Mea extracts of ACQ- and MCQ-treated wood performed similarly to wood treated with industrial ACQ solution and freshly prepared solution using cupric acetate. All treated wood had similar penetrations of Cu in wood during preservative treatment, Cu leaching from the treated wood in contact with water, corrosion of nails in contact with treated wood, and ability to protect wood from mold growth.     

Efficacy of wood preservatives formulated from okara with copper and/or boron salts

As a substitute for high-cost copper azole (CuAz) and alkaline copper quaternary (ACQ) wood preservatives, alternative wood preservatives were formulated with okara, which is an organic waste from the production of tofu, and copper chloride and/or borax. Each preservative was used in treatment of wood blocks in a reduced-pressure method to measure its treatability. The treated wood blocks were placed in hot water for 3 days to examine the stability of the preservatives against hot-water leaching. The preservatives successfully penetrated into wood blocks, probably due to the use of ammonium hydroxide as a dissociating agent. However, the stability of okara-based preservatives dropped as the concentration of acid in the solutions used for hydrolysis of okara increased. The treatability and leachability of the preservatives were not affected by hydrolysis temperature but were negatively affected by the addition of borax. Leached wood blocks treated with okara-based preservatives and exposed to decay fungi Gloeophyllum trabeum and Postia placenta over 12 weeks showed good decay resistance. Okara-based wood preservatives can protect wood against fungal attack as effectively as CuAz, and have potential for use as environmentally friendly wood preservatives.     

Distribution of heartwood extractives in hybrid larches and in their related European and Japanese larch parents: relationship with wood colour parameters

Heartwood is the most valuable part of larch timber when either natural durability or aesthetic aspects of the wood are required. Both properties are directly linked to chemical extractives and particularly to phenols. Based on a broad sample of trees (583) from European and Japanese larch and their interspecific hybrid, we investigated the variability in phenolic content, and particularly of two major compounds, Taxifolin (Tax) and Dihydrokaempferol (DHK), and their link with wood colour. At the individual wood sample level, phenolic contents ranged from 6.0 to 55.9 mg eq. Tax/g DW. Taxifolin was the most abundant constituent (range: 1.3–41.7 mg/g DW) compared with DHK (0.5–13.7 mg eq. Tax/g DW). A high variability among taxa, genotypes and individual trees within taxa and within trees was observed. Japanese larch had the highest amount of total phenols and of Taxifolin and European larch the lowest. For DHK, Japanese larch was the poorest compared with European larch. Hybrid larch had both a high content of Taxifolin and of DHK. Variability for colour parameters was on average weaker than for phenolic content but still large enough to show significant differences between taxa. Correlations between colour parameters and extractives were moderate to weak. At the mean genotype level, a good link (r > 0.51, p < 0.001) was found between a* (red–green axis in CIELAB) and total phenols and Taxifolin contents and between L* (Lightness) and DHK content (r > 0.54). The broad variability observed in this study at different levels for phenolics offers opportunities for breeders to genetically improve the quality of larch heartwood, in particular in relation to decay resistance.     

Spectrophotometric assay of a wood preservative, didecyldimethylammonium chloride (DDAC), in aqueous solution

A spectrophotometric assay based on the color reaction between didecyldimethylammonium chloride (DDAC) and 4-[4-(dipropylamino)phenylazo]-benzenesulfonic acid (propyl orange) was used for the determination of DDAC as a wood preservative. The assay was carried out using a propyl orange solution at pH 2.9. The visible absorbance spectrum of propyl orange showed an absorbance maximum at 510 nm, which decreased continuously with increasing DDAC concentration from 0 to 20 ppm. A linear correlation was observed at a DDAC concentration lower than 8 ppm. To apply this assay method to determine DDAC retention in treated wood, the influence of wood extractives on the assay was investigated. Wood extractives from sapwood and heartwood of Japanese cedar, Hinoki cypress, Japanese larch, and Western hemlock showed no influence on DDAC determination except in the case of heartwood from Japanese cedar and Hinoki cypress, which gave apparent DDAC concentrations higher than the actual values. However, it was also found that absorbance measurement at 477 nm solved this overestimation and gave precise values. It was concluded that this assay is a viable alternative to the current methods for DDAC determination.     

心材提取物和专用木材防腐剂作为木材保护剂的相对功效

本文调查了三种耐用木材(Afzelia africana J.E. Smith; Erythrophleum suaveolens (Guill & Perr.) Brenam. Syn. E guinensis G.Don. or Milicia excelsa (Welw) C.C. Berg. Syn. Chlorophora excelsa (Welw) Benth.)的心材提取物（在60%的甲醇中风干提取）和两种专用木材防腐剂（CCA和Penta）在暴露的土壤区组设计条件下，抑制三种木材腐朽菌(Coridopsis Polyzona Klotzch; Lenzites trabea; or Trametes cingulata Fr.)对见血封喉边材的侵袭的相对潜能，并测定其阈值。提取物和防腐剂的剂量分别是8.009、24.778、48.056、96.111、144.167 kg·m-3 ，样品的暴露处理时间与ASTM D1413-72规定的一致分别是14周和18周。结果显示：在阈值范围内，任何一种心材提取物或木材防腐剂在研究中对木材腐朽菌的抑制能力在0.01的显著水平下，差异显著。这些生物杀灭剂的相对功效是取决于真菌的种类。没有任何一种心材提取物或木材防腐剂（除在用最高的存留水平处理被侵袭的非洲毒箭木的条件下）对于被处理的木材能够授予"非常持久"等级。本土树种的心材提取物相对持久力的减少的可能原因是复杂的。在最高的存留量（144.167 kg·m-3）水平下，在0.05显著水平下每种心材提取物和任一种专用木材防腐剂（CCA和Penta）之间的功效差异不显著.     

Influence of carboxylic acids on fixation of copper in wood impregnated with copper amine based preservatives

The importance of copper/amine based preservatives is increasing. Leaching of copper from wood preserved with these solutions is still higher than leaching from wood impregnated with copper chromium ones. In order to decrease leaching, different carboxylic acids (octanoic, 2-ethylhexanoic, decanoic) were added to copper/amine/boron aqueous solutions. An experiment of leaching of copper from Norway spruce was performed according to the modified standard procedure (EN 1250). Results confirmed that carboxylic acids significantly improve copper fixation. The best fixation was determined in specimens impregnated with the preservative solutions consisting of copper, ethanolamine, boric acid and octanoic acid. From such wood, only 1.6% of copper was leached.     

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

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

Dependence of shear strength on wood properties in cultivated Larix sibirica

Abstract

Mechanical properties are very important in structural uses of wood. In the case of larch wood, shear strength (SS) may be a limiting property, because the wood is brittle and it splinters easily. In this study, SS of Siberian larch (Larix sibirica) wood was studied in relation to its axial and radial location and to some other wood properties in the part of the trunk that produces logs of good carpentry quality. SS increased by 21–23% from the pith to the outer heartwood at each studied height (butt, 4.5 and 9 m), and it was at its most approximately 7% higher at the butt than at the other studied heights. The main reason for the radial increase in SS was the increase in density caused by wood maturation, but other factors also affected SS, depending on the grouping mode (combined material, radial/axial location). An exception was sapwood, for which no factors affecting SS could be identified. Thus, sapwood may behave differently from heartwood regarding use, even unexpectedly. The results suggest that mature heartwood, but not juvenile wood and sapwood, of Larix sibirica should primarily be used in products that require high SS.     

Acetaldehyde emission from wood induced by the addition of ethanol

A mechanism of acetaldehyde emission from wood induced by the addition of ethanol was proposed. It is known that acetaldehyde generation is due to the oxidation of ethanol via a metabolic process involving alcohol dehydrogenase (ADH) in living bodies. However, it remains unclear whether the enzymatic alcohol oxidation is applicable to wood. We investigated possible factors of wood parts, conditioning, storage sites, and heating and sterilization treatments on acetaldehyde emission using the syringe method and HPLC analysis. We reconfirmed that acetaldehyde emission was observed only when ethanol was added to wood. Greater acetaldehyde emissions were obtained in heartwood compared to sapwood in both Japanese cedar (Cryptomeria japonica D. Don) and Japanese cypress (Chamaecyparis obtusa Endl.) specimens. In addition, an acetaldehyde conversion rate of 1–2 mol% was determined in green cedar heartwood samples, while, conversely, air-dried cedar heartwood samples showed 4–5 mol%. Ethylene oxide gas sterilization had the effect of decreasing acetaldehyde emission on air-dried wood, but not on green wood. Autoclave sterilization could completely prevent acetaldehyde emissions from both green and air-dried wood. These results suggested that an original ADH in wood and an attached ADH from the outside via microorganisms onto wood were assumed to be the primary causes of acetaldehyde emissions from wood induced by the addition of ethanol.     

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     

季铵盐类化合物(QAC)在木材防腐中的应用

主要综述了季铵盐类化合物(QAC)在用作木材防腐剂时的耐腐性、抗流失性及其与木材的结合机理等方面的研究概况,分析了实验室耐腐性和野外实验耐腐性结果不一致的原因。此外也介绍了对季铵盐进行改性处理方面的一些研究进展。     

Adhesive performance of woods treated with alternative preservatives

The extended use of woods treated with traditional or alternative preservatives for exterior applications requires an assessment of wood adhesive performance. This study attempts to evaluate the performance of wood adhesives for woods treated with various waterborne preservatives. Two softwood species, i.e. Korean pine (Pinus koraiensis Sieb. et Zucc.) and Japanese Larch (Larix leptolepis [Sieb. et Zucc.] Gordon) were treated with copper–chrome–arsenic (CCA), CB-HDO, or copper azole (CY), and then bonded with four different wood adhesives such as urea–melamine–formaldehyde (UMF) resin, melamine–formaldehyde (MF) resin, phenol–formaldehyde (PF) resin, and resorcinol–formaldehyde (RF) resin. The performance of these adhesives was evaluated by measuring the dry shear strength of adhesive-bonded wood block on compression. Both UMF and MF resins produced a relatively strong adhesive strength for CY-treated pine and larch woods. The PF resin also produced good bond strength when bonded with either larch wood treated with CY or pinewood treated with CB-HDO. The best result was obtained when the CB-HDO-treated woods were bonded with RF resin. For a better bond strength development, a proper combination of adhesive, preservative, and wood species should be selected by taking into consideration of the characteristics of these three parameters as well as their interactions.     

Effect of adding steam-exploded wood flour to thermoplastic polymer/wood composite

The effect of steam-exploded wood flour (SE) added to wood flour/plastic composite was examined using SE from beech, Japanese cedar, and red meranti and three kinds of thermoplastic polymer: polymethylmethacrylate, polyvinyl chloride, and polystyrene. Addition of SE increased the fracture strength and water resistance of the composite board to an extent dependent on the polymer species and the composition of wood/SE/polymer. However, water resistance decreased with the increasing proportion of SE when SE meranti was added. Effects of the wood species of SE on the properties of resulting board were small. An increased moisture content of wood flour or SE (or both) increased the variation of board performance.     

Leaching of toxic elements from spruce treated with ammoniacal solutions of copper-zinc-arsenic preservatives

Summary White spruce (Picea glauca) was treated with ammoniacal solutions of various preservatives containing copper, zinc, and arsenic. The wood was then leached in a severe accelerated test and the amount of copper, zinc, and arsenic lost from the wood was determined. The leachability of arsenic depended on the preservative formulation; when the ratio of metal oxide to arsenic oxide was less than 1.25, 35 to 67% of the arsenic was lost, but when this ratio was greater than 1.25 only 1 to 15% of the arsenic was lost. Only small amounts (1 to 4%) of copper and zinc were leached out using any of the tested formulations. Temperature of fixation had only a slight influence on leaching of copper, zinc or arsenic.The technical assistance of Mr. C. D. Ralph is appreciated.     

长白落叶松提取物对木材防腐作用的研究

以长白落叶松心材、边材及树皮为原料,分别用乙醚、氯仿、丙酮、甲醇和水5种溶剂对其进行提取,采用滤纸片法研究了不同溶剂提取物分别对白腐菌和褐腐菌的抑菌性能,发现心材的甲醇提取物和丙酮提取物对白腐菌有较好的抑制效果,树皮的水提取物对2种菌都有较好的抑制效果.并研究了这两种提取物在室内对木材的防腐性能,借助扫描电子显微镜(SEM)照片观察了木材腐朽后菌丝生长的情况,与常用木材防腐剂酸性铬酸铜(ACC)进行了对比,结果显示:心材的甲醇提取物对白腐菌的抑制效果较好;而树皮的水提取物对褐腐菌抑制效果较好.     

房屋建筑材用防腐剂的毒性试验

通过对十八种药剂配方(其中水溶性配方15种、油溶性配方3种)对木腐菌的毒性试验及对初筛后的配方进行流失后毒性试验,结果表明,水溶性配方中的铜铬砷即CCA_3、CCA_4、CCA_5,铜铬硼即CCB_5配方,以及油溶性配方中的P—B剂的毒性较大。     

Variation in the decay resistance of larch to fungi

? Decay resistance of larch (Larix sp.) to fungi was evaluated on heartwood samples belonging to 3 species (L. decidua, L. kaempferi and their hybrid), 3 races of European larch (polonica, sudetica and alpine), 13 wood lots (populations) and 313 trees.

? Larch wood appeared, on average, as moderately durable although a high variability was observed. At the sample level as well as at the mean individual tree level, durability ranged from class 1 to 5 according to EN 350-1 standard. At the population level, larch wood varied from ‘durable’ to ‘slightly durable’. Genetics played a major role in decay resistance at the species, provenance and tree levels. Environmental factors such as the position of heartwood samples and the age of trees were also identified as a source of variability.

? The most durable wood was not necessarily from old native alpine stands of European larch: some young larches from faster growing lowland origins also produced durable wood.

? Genetic improvement of larch wood durability appeared therefore likely by the selection of the best populations for decay resistance as well as from the selection of individuals.