Screening of properties of modified chitosan-treated wood

Chitosan is a biopolymer derived from chitin in crustacean shells. Over the past decade it has been studied as an environmentally benign wood-protecting agent. It is assumed to act as a fungi-stat against a wide range of fungi and even as a fungicide at higher concentrations. This study investigated the properties of wood treated with modified chitosan of different molecular weights. Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) samples were impregnated with two chitosan solutions differing in their average molecular weights. The chitosan solutions were depolymerized by nitrous acid to one solution of high molecular weight and one solution of low molecular weight with a concentration of 5% (w/v). The results show changes in sorption properties, antifungal properties, fire-retardant properties and mechanical properties of modified chitosan-treated wood. Heat-modified, chitosan-treated wood showed similar properties to chitosan-treated wood, except for brownish coloration, enhanced hydrophobation, and slightly reduced antifungal and fire-retardant properties. The modulus of rupture and hardness showed little or no change. The modulus of elasticity of the heat-modified, chitosan-treated wood increased by 27% compared with untreated wood.     

Screening of properties of modified chitosan-treated wood

Abstract

Chitosan is a biopolymer derived from chitin in crustacean shells. Over the past decade it has been studied as an environmentally benign wood-protecting agent. It is assumed to act as a fungi-stat against a wide range of fungi and even as a fungicide at higher concentrations. This study investigated the properties of wood treated with modified chitosan of different molecular weights. Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) samples were impregnated with two chitosan solutions differing in their average molecular weights. The chitosan solutions were depolymerized by nitrous acid to one solution of high molecular weight and one solution of low molecular weight with a concentration of 5% (w/v). The results show changes in sorption properties, antifungal properties, fire-retardant properties and mechanical properties of modified chitosan-treated wood. Heat-modified, chitosan-treated wood showed similar properties to chitosan-treated wood, except for brownish coloration, enhanced hydrophobation, and slightly reduced antifungal and fire-retardant properties. The modulus of rupture and hardness showed little or no change. The modulus of elasticity of the heat-modified, chitosan-treated wood increased by 27% compared with untreated wood.     

铜-季铵盐复配木材防腐剂的防腐性能

在实验室内采用常规的真空－加压法浸注试件，土壤木块法进行防腐试验，检验了铜－季铵盐类防腐剂（FFJ－1、FFJ－2和FFJ－3）对白腐采绒革盖菌[Coriolus versicolor(L.ex Fr.)Quel.]和褐腐绵腐卧孔菌[Poria placenta(Fr.)Cooke.]的防腐性能，结果表明：在较低的保持量下，都有较好的防腐效果。与百菌清（可湿性粉剂）、五氯酚钠、三唑酮相比较，它们对白腐菌的防腐性能与百菌清相近，批五氯酚钠和三唑酮好。     

CMC系列防腐剂对毛竹材的防霉效果

以3～4年生新伐毛竹为试材,以青霉、木霉、黑曲霉为试菌,与常用的竹材防霉剂硼酸(HBO3)、百菌清等进行比较,对壳聚糖金属配合物(CMC)系列的壳聚糖铜配合物(CCC)、壳聚糖锌配合物(CZC)的防霉性能进行测试.结果表明:CCC和百菌清对木霉、青霉、黑曲霉防治效果均优于CZC、壳聚糖和硼酸;相比之下,CCC对青霉防治效果优于百菌清,而百菌清对木霉防治效果优于CCC.     

植物精油对木材霉变菌的抑菌效力研究

【目的】植物精油是一类安全环保且具有抑菌特性的天然产物,在木材霉变防治领域的应用潜力很大。开展植物精油对我国常见木材霉菌及变色菌的综合抑菌效力的研究,可为天然环保型木材霉变防治剂的开发提供重要依据。【方法】配制经植物精油修正的马铃薯葡萄糖琼脂培养基,通过评价霉变菌在培养基中的生长状况,对比分析19种植物精油对6种木材霉变菌的抑菌效力。【结果】在体积分数为0.05%的条件下,19种植物精油对黑曲霉Aspergillus niger、桔青霉Penicillam citrinum、绿色木霉Trichoderma viride、可可球二孢Botryodiplodia theobromae、串珠镰刀菌Fusarium moniliforme和链格孢霉Alternaria alternata的抑菌效力分别为0~100%、0~100%、0~100%、0~100%、11%~100%和20%~100%。聚类分析表明,肉桂、丁香花和百里香精油的综合抑菌效力最高,在体积分数0.05%的条件下对6种霉变菌的抑菌效力均达到100%,而尤加利、甜橙和松树精油的综合抑菌效力最低。相关分析表明,植物精油对6种霉变菌的抑菌效力之间均表现出显著相关性(P=0.01),其Pearson相关系数为0.777~0.959。【结论】不同植物精油的抑菌效力之间表现出较大差异,肉桂、丁香花和百里香精油是可以用于木材霉变防治的较优品种。     

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     

壳聚糖性能及其在木材工业中的应用

壳聚糖是一种来源广泛、安全无毒的天然高分子碱性多糖,独特的化学结构使其具有许多优异的特性,在生物医学、服装纺织、农业等领域都有不错的应用。目前,有关壳聚糖在木材保护上的利用也取得一定的研究成果。文中介绍了壳聚糖的性能及其在木材工业上的基本应用,重点阐述归纳了壳聚糖在木材防腐、木材阻燃、木材胶黏以及木材固色4个方面的研究现状,展望了壳聚糖在木材工业领域应用中的发展趋势,旨在进一步推动壳聚糖在木材工业中的应用研究。     

Evaluation of factors that have an influence on the fixation of chitosan in wood

When using chitosan as an antifungal agent in wood it is important to understand which factors contribute to a higher fixation ratio to optimize the utilization of chitosan, the active component. Small pine samples were impregnated with chitosan solutions varying in molecular weight, concentration, pH, polymerization agent, acid and degree of deacetylation. Different post-treatments such as time, temperature, moisture content and the effect of present air were applied to the samples to evaluate the effect on the relative retention. After impregnation, the samples, with a volume of 1.5 cm³, were leached in separate test-tubes according to EN-84. The samples were prepared in a paired design where both samples were impregnated, but only one was leached. Both leached and unleached samples were analysed for their chitosan content, and the relative ratio was used as a measure for the relative retention of chitosan during leaching. The results from these trials show that pH in the range of 5.1-5.9 is favourable. The molecular weight should be as high as possible yet able to penetrate the wood structure, and the use of acetic acid gives far better fixation than the use of hydrochloric acid.     

壳聚糖金属配合物处理后竹材的防褐腐作用及力学性能

以4年生新伐毛竹为试材,以褐腐菌棉腐卧孔菌为试菌,对壳聚糖铜配合物(CCC)、壳聚糖锌配合物(CZC)及相应的金属盐(氯化锌)和铜铬硼(CCB)、ACQ处理材的耐腐性能、力学性能及胶接性能进行研究.结果表明:1) CCC处理的竹材对棉腐卧孔菌的耐腐性能不及CCB和ACQ处理材;但是,随着CCC处理浓度的增加,处理材耐褐腐性能明显增加,当处理材中金属离子保持量达到5.141 kg·m-3时,腐朽后质量损失低于6.1%.2) CZC处理毛竹试材的耐腐效果低于CCC、CCB和ACQ,略高于氯化锌处理材,当CZC中金属离子保持量高于5.091 kg·m-3时,处理材的质量损失在26.4%～29.0%之间.3) 同素材(未处理材)相比,经防腐剂处理后的竹材力学性能及胶接性能均有不同程度下降,尤其是CCB处理材.在所测指标中,抗弯弹性模量和抗弯强度下降最明显,横纹抗压强度和胶接强度除CCB外变化不大.     

Evaluation of decay resistance of wood products made from borax-impregnated wood and bonded with a formaldehyde-free cornstarch and tannin adhesive

? At present, the production of wood composites mainly relies on the petrochemical-based and formaldehyde-based adhesives such as phenol-formaldehyde (PF) resins and urea-formaldehyde (UF) resins, which are non-renewable and therefore ultimately limited in supply.

? This paper concerns the decay resistance of wood products bonded with a new, environment-friendly adhesive derived from abundant and renewable cornstarch and tannin. To improve the total resistance of the composite against both Coriolus versicolor and Coniophora puteana rot fungi, borax (di-sodium tetraborate) was added in proportions of 0.5%, 1% and 2% (w/w) to the cornstarch-tannin adhesives.

? The results show that increasing the concentration of borax in the adhesive decreased the mechanical properties of the composite. The best way to avoid this problem was to use wood impregnated with borax.

? Biodegradation studies were conducted on new composites, first without any treatment, followed by borax at 0.5% aqueous solution treatment. The results show that wood impregnated with borax, in the presence of tannin and sodium hydroxide in the adhesive improves the total resistance of the wood composite against both Coriolus versicolor and Coniophora puteana rot fungi.

     

The modification of wood by treatment with low molecular weight phenol-formaldehyde resin: a properties enhancement with neutralized phenolic-resin and resin penetration into wood cell walls

To enhance dimensional stability and biological properties, low molecular weight phenolic resins of a conventional alkaline type and neutralized type were impregnated into Japanese cedar wood (Cryptomeria japonica D. Don) and heat-cured. The treatment with the neutralized type resin retained the original wood color, whereas the alkaline treatment changed the color of wood to red-brown. The concentrations of the resin solutions and the weight gains due to the resin loading of wood after treatment were highly correlated, and the target resin loading could be assessed from the solution concentration. A high dimensional stability of 60% antiswelling efficiency was attained when both types of resins were impregnated at about 30% resin loading and no significant difference was recognized between the two. To suppress decay attack from brown-rot and white-rot fungi, 15% and 10% resin loading due to treatment was required for the neutralized and alkaline types of phenolic resins, respectively. The penetration of resin into wood cell walls was investigated by means of light microscopy, Scanning Electron Microscopy (SEM), and Electron Probe X-ray Microanalysis (EPMA). A m-Bromophenol-formaldehyde resin of three levels of an average molecular weight was used to detect the presence of resin by bromine signals. The phenolic resins with low and medium molecular weights (290 and 470) were shown to penetrate into the cell walls the furthest, thereby contributing to the enhancement of dimensional stability and decay resistance in the resin-impregnated wood. Also, for phenolic resin with a high molecular weight (820), only the resin components of low molecular weight appeared to be present in the walls, making very little contribution to the dimensional stability.     

Evaluation of factors that have an influence on the fixation of chitosan in wood

Abstract

When using chitosan as an antifungal agent in wood it is important to understand which factors contribute to a higher fixation ratio to optimize the utilization of chitosan, the active component. Small pine samples were impregnated with chitosan solutions varying in molecular weight, concentration, pH, polymerization agent, acid and degree of deacetylation. Different post-treatments such as time, temperature, moisture content and the effect of present air were applied to the samples to evaluate the effect on the relative retention. After impregnation, the samples, with a volume of 1.5 cm³, were leached in separate test-tubes according to EN-84. The samples were prepared in a paired design where both samples were impregnated, but only one was leached. Both leached and unleached samples were analysed for their chitosan content, and the relative ratio was used as a measure for the relative retention of chitosan during leaching. The results from these trials show that pH in the range of 5.1–5.9 is favourable. The molecular weight should be as high as possible yet able to penetrate the wood structure, and the use of acetic acid gives far better fixation than the use of hydrochloric acid.     

木材白腐机理研究进展

白腐菌是木材的主要腐朽菌之一，白腐菌菌丝在细胞内形成多种降解酶主要是木素降解酶，次则是纤维素降解酶及半纤维素降解酶，以降解细胞壁物质中的木素、半纤维素及纤维素，作为木腐菌的营养。由于这些木材组成的降解，必然改变木材的化学及物理性质。近年来，在白腐菌的营养需求、降解酶传递途径，对木材主要组成酶降解机理及对材性的影响，产酶的分子遗传等领域的研究均取得一定进展，可望不久将来能利用生物工程改变白腐菌基因，     

壳聚糖处理木材表面的材色变化及对表面加工的影响

壳聚糖是一种无毒害且可再生的天然讷发子材料，可用于木才表面改性处理。本文通过对杉木边材、心材和毛白杨边材表面涂饰不同浓度的壳聚糖乙酸溶液，测定分析处理前后的木才材色变化。结果表明：不同深度壳聚糖处理木材表面，处理产后总体色差随深度的升高而增加，其它色度学参数略有变化；壳聚糖处理木材表面的最佳深度是２．０％，处理后对木才表面的进一步着色或涂饰无大影响。     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.     

壳聚糖前处理染色木材耐光性的研究

对壳聚糖前处理与未处理（对照）染色木材耐光性的研究表明,山杨等６种壳聚糖处理与未处理木材用同一染料染色并辐射１０小时后,处理材色差均比未处理材低;经壳聚糖前处理与未处理的安息香木才,用四种不同染料染色,染色材耐光性优于未处理材,但随染料种类不同略有差异。     

壳聚糖及其金属配位聚合物在木材工业中的应用现状与展望

壳聚糖(chitosan)是从虾、蟹等甲壳动物中提取的一种天然碱性高分子多糖,壳聚糖易与过渡金属及稀土金属配位形成壳聚糖金属配位聚合物[chitosan metal complexes(CMC)],壳聚糖及壳聚糖金属配位聚合物是目前研究广泛的一类新型高分子生物材料,近年来的研究表明壳聚糖及壳聚糖金属配位聚合物在木材工业中有着广泛的应用前景,例如作为环保型木材防腐剂,促进木材防腐工业的持续发展。笔者介绍了其基本应用,重点报道其在木材染色、木材保护及用于木质材料胶合方面的应用及研究进展。     

Antifungal activity of Liriodenine from Michelia formosana heartwood against wood-rotting fungi

Wood-rotting fungi lead to great economic losses of lignocellulosic materials. The influence of extractives on the decay resistance of Michelia formosana wood and the antifungal activities of heartwood extract and its constituent against wood-rotting fungi were evaluated. Results revealed that extractives had a strong influence on the decay resistance of M. formosana heartwood. The unextracted heartwood block was resistant to fungi, while the extracted heartwood block was not. Antifungal activities of ethanolic extract from heartwood were assessed; results revealed that the ethanolic extract possessed good antifungal activity against wood-rotting fungi. The ethanolic extract was further separated into four fractions including n-hexane-soluble fraction, ethyl acetate-soluble fraction, n-butanol-soluble fraction, and water-soluble fraction. Among these fractions, the n-hexane-soluble fraction exhibited the best antifungal ability. An alkaloid, liriodenine, was isolated from the active n-hexane-soluble fraction. IC₅₀ values of liriodenine against the white-rot fungi Lenzites betulina and Trametes versicolor were 0.76 and 3.50?μg/mL, respectively. IC₅₀ values of liriodenine against the brown-rot fungi Laetiporus sulphureus, Gloeophyllum trabeum, and Fomitopsis pinicola were all lower than 2.0?μg/mL. Results indicated that liriodenine exhibited a broad spectrum of antifungal activity and great potential to develop as an environmentally benign fungicide for the preservation of lignocellulosic materials.     

Antifungal and antitermitic activities of wood vinegar from oil palm trunk

We evaluated the antifungal and antitermite activities of wood vinegars produced from oil palm trunk. The wood vinegars were produced at three different pyrolysis temperatures, 350, 400, and 450 °C. Antifungal activities of vinegars were evaluated using a Petri dish bioassay with 0.5, 1.0, and 1.5% (v/v) against a white-rot fungus, Trametes versicolor, and a brown-rot fungus, Fomitopsis palustris. Antitermite activities were tested using a no-choice bioassay method for Coptotermes formosanus with 2.5, 5.0, 7.5, and 10.0% (v/v). All the wood vinegars exhibited antifungal activities against T. versicolor. In particular, the wood vinegar produced at 350 °C resulted in complete inhibition of T. versicolor growth at 1.0 and 1.5%. However, higher concentrations were required to obtain growth inhibition of F. palustris. All the wood vinegars exhibited antitermite activity to C. formosanus workers in the no-choice experiment at relatively high concentrations. For instance, 10% concentration was required to achieve 100% mortality against C. formosanus at all production temperatures. The lowest mass loss of the treated filter paper of 11.75% was obtained with a 350 °C—10.0% combination.     

Antifungal activity of essential oils isolated from Egyptian plants against wood decay fungi

The essential oils of eighteen Egyptian plants were extracted by hydrodistillation and their chemical compositions were analyzed by GC-MS. The antifungal activity of the isolated oils was evaluated against two wood decay fungi Hexagonia apiaria and Ganoderma lucidum in vitro. The essential oil of Artemisia monosperma showed the highest inhibitory effect against H. apiaria (EC₅₀ = 31 mg L^?1) and G. lucidum (EC₅₀ = 53 mg L^?1). The results of in vitro tests indicated that the essential oils of Cupressus sempervirens, Citrus limon, Thuja occidentalis, Schinus molle, A. monosperma and Pelargonium graveolens were the most potent inhibitors against both fungi. These six oils caused significant reduction of wood mass loss of Scots pine sapwood after 6 weeks of fungal exposure. The oil of C. limon revealed the highest reduction of wood mass loss caused by H. apiaria, while A. monosperma oil displayed the highest reduction of wood loss caused by G. lucidum. These results support the potential use of essential oils for wood protection against decay fungi.