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.     

木质纤维成分的乙酸分离方法及表征

研究了一种用含有少量硫酸的乙酸溶液分离杨木成分的方法。考察了反应时间、乙酸浓度、液比和催化剂浓度对木材成分分离的影响。对分离出的木材三种成分进行了表征。结果表明,分离杨木成分的较佳条件为:硫酸浓度0.3%,液比6,反应时间3h和乙酸浓度90%。残渣的主要成分是α-纤维素和半纤维素。水不溶沉淀物(乙酰化木质素)的重均分子量分布在341到253之间,分散性系数分布在1.1到1.2这一窄范围内。糖分析结果表明,可溶性成分主要来源于半纤维素,以单糖形式存在。     

Acetylation of wood in combination with polysiloxanes to improve water-related and mechanical properties of wood

Scots pine sapwood was acetylated with ethyltriacetoxysilane using acetic acid as a solvent and sulfuric acid as a catalyst. A weight percent gain (WPG) of 14 % and cell wall bulking of 7 % were obtained after 5 h of reaction time. Pine specimens were acetylated with acetic anhydride in the presence of 1 % ethyltriacetoxysilane, dihydroxy-functional siloxane, acetoxy-functional siloxane, amino-functional siloxane and non-functional siloxane, respectively. Acetoxy-functional siloxane induced the greatest reduction in water uptake with a water repellent effectiveness after 24 h of up to 62 % as compared to acetylated wood. WPG and cell wall bulking increased compared to solely acetylated wood with increasing concentrations of acetoxy-functional siloxane in acetic anhydride; anti-shrink efficiency, however, did not increase. Fungal resistance of pine sapwood and beech as well as mechanical strength properties did not change when 20 % acetoxy-functional siloxane was added to acetic anhydride compared to solely acetylated specimens.     

芍药种子含油率与脂肪酸成分研究

[目的]本文对芍药种子含油率、脂肪酸成分及含量进行了探讨,为芍药开发成油料植物提供参考。[方法]选取芍药36个栽培品种和1个野生居群为样本,采用索氏提取法提取种子油脂并测定含油率,用气相色谱—质谱联用仪(GC-MS)对提取的籽油成分进行分析。[结果]表明:芍药36个栽培品种和1个野生居群种子平均含油率为20.20%。芍药籽油主要含有豆蔻酸、棕榈酸、棕榈一烯酸、硬脂酸、油酸、亚油酸、亚麻酸和花生酸8种脂肪酸,其中,亚麻酸含量最高,平均达34.14%,其次为油酸和亚油酸,这3种不饱和脂肪酸的含量占全部脂肪酸的93.37%。芍药籽油脂肪酸含量变化相对稳定,各脂肪酸成分的变异系数从大到小依次为亚油酸(13.90%)油酸(13.51%)亚麻酸(10.71%)棕榈酸(0.18%)硬脂酸(0.09%)花生酸(0.002%)、棕榈一烯酸(0.002%)豆蔻酸(0.00%)。[结论]芍药种子含油率高,富含亚麻酸、亚油酸和油酸,且含量相对稳定,变异很小,具有开发为高含量亚麻酸食用油潜力。     

Preparation of acetylated wood meal and polypropylene composites I: acetylation of wood meal by mechanochemical processing and its characteristics

Wood meals of Sugi (Cryptomeria japonica D.Don) passing 2.0 mm and retained on 1.0 mm mesh screens were milled along with acetic anhydride (AA) and pyridine as a catalyst in a high-speed vibration rod mill at ambient temperature. The weight percent gain (WPG) of the chemically modified wood was calculated based on the yield after washing with deionized water. The effects of amounts of AA and catalyst added, pulverization time, and saponification of the acetylated wood on WPG were examined. In addition, FT-IR analysis, and water vapor adsorption and desorption tests were performed as functions of the WPG. Increases in WPG, the acetyl contents of the acetylated wood after saponification, changes in the FT-IR spectra after pulverization, and the water vapor sorption isotherms showed that the one-step acetylation systematically modified the hydroxyl groups of the wood into acetyl groups. Up to 38 % WPG was obtained at 100 phr AA and 15 phr catalyst, and 120 min pulverization. Pulverization time and the amounts of AA and catalyst added to the wood meals could be adjusted to obtain acetylated wood meal with the desired WPG. These demonstrated that the mechanochemical acetylation is a method to prepare acetylated wood meals with high WPG at less reaction time and required AA addition.     

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.     

Dependence of reaction kinetics and physical and mechanical properties on the reaction systems of acetylation II: physical and mechanical properties

Acetylation of wood was carried out in acetic anhydride only, acetic anhydride/xylene 1:1 (v/v), and acetic anhydride/pyridine 4:1 (v/v) solutions. The antishrink efficiency (ASE), hygroscopic properties, vibrational properties, and bending strength were compared among the three reaction solutions. The ASE was a simple function of weight gain (WG); the equilibrium moisture content at a given WG differed among the reaction solutions. Based on this fact and the results of repeated water soaking and oven-drying tests, it was found that the bulking effect was a major factor, and that decreased hygroscopicity contributes only slightly to the dimensional stabilization by acetylation. The difference in equilibrium moisture content among reaction solutions appears more significant in block samples than wood meal, probably due to the fiber-to-fiber bonds in the former. The tendencies for change in the specific Youngs modulus and the loss tangent differed among reaction solutions, whereas in the static bending test the difference was not marked.Part of this report was represented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

安徽地区华东野核桃果实特征和坚果品质的初步评价

[目的]探究华东野核桃果实性状、核仁成分及其相关性,为其资源的开发和综合利用提供依据。[方法]本研究以皖南华东野核桃资源为对象,测定其鲜果单果质量、果皮厚度与坚果单果质量、壳厚度、出仁率等果实性状及坚果核仁成分,分析其相关性。[结果]华东野核桃果实性状具有丰富的变异,大部分变异系数大于10%,其中,坚果壳厚度变异系数最大为43.92%。对坚果核仁成分的测定表明:核仁中脂肪含量最高,蛋白质次之,总糖含量较低;对脂肪组分的进一步分析可知,其不饱和脂肪酸含量较高,达92.68%。利用相关性分析,发现坚果单果质量与核仁脂肪含量呈显著正相关。利用主成分分析对华东野核桃果实性状及核仁成分的综合分析及评价发现,单株编号10和8的鲜果大小及不饱和脂肪酸含量在所受试单株中综合表现最好,可作为进一步育种的遗传资源。[结论]本研究首次报道华东野核桃果实核仁成分,发现其核仁脂肪酸含量高于薄壳山核桃、山核桃,且不饱和脂肪酸含量也高,表明其核仁是值得开发的一种新食品资源。该研究结果为华东野核桃资源的综合开发与利用提供了数据支持。     

A novel method of acetylation of wood using supercritical carbon dioxide

Sugi heartwood was acetylated with acetic anhydride in supercritical carbon dioxide (CO₂) (120°C or 130°C, 10–12 MPa). As a result, the weight percent gain increased with increasing acetylation time up to 16%–20% at 1 h and 24%–28% at 24 h. The antiswelling efficiency of the acetylated specimens reached 75%–80% at 3–4 h of acetylation. It is supposed that the acetylation in supercritical CO₂ has a high bulking effect compared with liquid-phase and vapor-phase acetylation with uncatalyzed acetic anhydride. The results showed that the acetylation progressed rapidly because supercritical CO₂ and acetic anhydride formed a single phase at more than 90°C, and the acetic anhydride reached the reaction sites in the wood quickly.     

Chemical modification of wood: A short review

Abstract

For most markets for wood, it is used without any treatments or modifications. When wood is used in adverse environments, it may be treated with chemicals to help prevent decay, improve water resistance, reduce the effects of ultraviolet radiation or increase fire retardancy. Many of these treatments involve the use of toxic or corrosive chemicals that can harm the environment. Chemical modification of wood provides an alternative by providing protection against water, decay, UV and thermal degradations by bonding chemicals to the cell wall polymers that do not leach out. Dimensional stability and decay resistance are two major properties that can be greatly improved by simple reactions with acetic anhydride.     

Properties of oriented strand board made from Betung bamboo (Dendrocalamus asper (Schultes.f) Backer ex Heyne)

Bamboo has gained increasing attention as an alternative raw material for use in the manufacture of composite boards. Three-layer OSBs were made using Betung bamboo (Dendrocalamus asper (Schultes.f) Backer ex Heyne) strands to evaluate the effects of strand length and pre-treatment techniques on the physical, mechanical, and durability properties. Three different strand lengths, namely 50, 60, and 70?mm, were prepared. Prior to the manufacture into OSB, the strands were immersed in cold water for 24?h and in 6% acetic anhydrides solution for 48?h. The OSBs were fabricated using 5% MDI resin based on the strand dry weight. The results indicated that MOR and MOE values in perpendicular to the grain direction were much influenced by strand length. The dimensional stability of OSB was slightly improved by immersing the strands in acetic anhydride solution. Immersing strands in cold water and acetic anhydride solution improved the resistance of OSB against subterranean termite (Macrotermes gylvus) attack under the adopted experimental condition. All OSB parameters manufactured in this experiment were better than the minimum requirement of CSA 0437.0 (Grade O–2) standard.     

高锰酸钾氧化马鞭草烯酮的研究

考察了反应温度、反应时间、高锰酸钾用量、乙酸与水溶液体积比对高锰酸钾氧化马鞭草烯酮制备低蒎酮酸的影响,研究结果表明:控制原料与高锰酸钾的物质的量比1∶4,反应温度10℃,反应时间2h,乙酸与水溶液体积比10∶1,得到低蒎酮酸的收率77％.讨论了硅胶作为载体对此实验的影响,结果显示使用硅胶-高锰酸钾作为氧化剂,目标产物的...     

玉米秸秆基吸油材料的制备与表征

以玉米秸秆(RCS)为原料,经氨水预处理得预处理玉米秸秆(PCS),再经乙酸酐酯化改性制备改性玉米秸秆(ECS)吸油材料,并考察不同酯化条件对产物吸油性能的影响。结果表明:RCS、PCS(预处理6 h)对0~#柴油的吸收倍率分别为1.90和4.43 g/g;以冰乙酸为溶剂,冰乙酸与乙酸酐质量比为1∶1,秸秆与冰乙酸-乙酸酐混合液的质量比为1∶15,催化剂浓硫酸用量为4.5%(以秸秆质量计),反应温度为110℃条件下,酯化反应5 h所得改性产物ECS的吸油率可达9.03 g/g,且ECS疏水性和漂浮性能均得到显著改善。采用XRD、FT-IR、SEM和BET等方法对预处理前后及酯化改性后秸秆进行了分析与表征。结果表明:酯化反应已顺利进行,酯化改性后秸秆呈非晶态,ECS呈均匀的介孔结构,介孔及粗糙表面的出现提高了材料的吸油率和漂浮性能。     

Non-uniform reaction of solid wood in vapor-phase acetylation

To clarify the non-uniform reaction of wood during vapor-phase acetylation, spruce wood blocks were exposed to acetic anhydride vapor at 120°C. Weight percent gain (WPG) due to the acetylation was estimated from the equilibrium moisture content at 25°C and 60% relative humidity. The diffusion of reagent vapor was much faster along the longitudinal direction than along the tangential direction. When the end surface was exposed to the reagent vapor for 48?h, 20% WPG, which was known to have sufficient stability and durability, was achieved to a depth of 42.5?mm. However, this depth was only 6.5?mm when the straight-grain surface was exposed. The reaction profiles were successfully approximated using reaction time (t), reaction rate (k′), delay time (t _d′), and a parameter n reflecting the diffusion-controlled reaction. The t _d′ value increased almost linearly as the depth increased from the surface. The k′ value ranged from 0.02 to 0.03?h^?1, regardless of the depth and direction of diffusion. The n value decreased with an increase in the depth and approached 1–2. These values enabled the prediction of the degree of acetylation at any reaction time and positions of wood during vapor-phase acetylation.     

Analysis of the water vapour sorption isotherms of thermally modified acacia and sesendok

Abstract

Two Malaysian hardwoods, acacia (Acacia mangium) and sesendok (Endospermum malaccense), that had been subjected to oleo-thermal modification were studied to determine their sorption isotherm behaviour using a dynamic vapour sorption apparatus. All the specimens were thermally modified using palm oil at three different temperatures (180, 200 and 220°C) and three different times (1, 2 and 3 h). The results showed that there was a reduction in equilibrium moisture content at each target relative humidity due to the heat treatment, but that the two wood species showed different behaviour in this respect. The adsorption isotherms were analysed using the Hailwood and Horrobin model, with excellent fits to the experimental data. The monolayer water and polylayer water were both reduced at a range of relative humidity values of the treated samples, although behaviour between the two wood species differed. Heat treatment resulted in an increase in hysteresis ratio, which was probably due to the increase in matrix stiffness of the cell walls.     

Solid-state13C-NMR analysis of size components in handsheets prepared by fatty acid soap size-alum systems

The mechanism of paper sizing in fatty acid soap size-alum systems was studied by structural analyses of the size components in handsheets prepared with¹³C-labeled fatty acid soap size. Patterns of sizing performance and aluminum content of the handsheets were similar to those for the rosin soap size-alum sizing systems, although the patterns of calcium content were different. Solid-state¹³C-nuclear magnetic resonance analysis of the handsheets revealed that fatty acid calcium salt was the predominant size component in the handsheets prepared using tap water. This calcium salt is formed from the fatty acid soap size (fatty acid potassium salt) by ion exchange with calcium ion in pulp suspensions and retained on pulp fibers through aluminum compounds originating from alum added. On the other hand, when deionized water was used, free fatty acid was the major component in the handsheets. Fatty acid aluminum salt was present as a minor component in the handsheets prepared in both tap water and deionized water systems. Therefore, all size components (i.e., fatty acid calcium salt, free fatty acid, fatty acid aluminum salt) seem to contribute to the appearance of sizing features.This research was presented in part at the 64th Pulp and Paper Research Conference of Japan TAPPI, Tokyo, June 1997     

巯基纤维素处理重金属废水研究

纤维素与硫代乙醇酸在乙酸酐和乙酸介质中发生酯化反应，合成巯基纤维素(SC)。含重金属的废水中加入碱调节废水pH值至9～10，静置、过滤。滤液用酸调pH值至5～7后流经SC管，去除废水中镉、铅、铜、汞等重金属。SC用稀盐酸淋洗再生。对使用和再生条件及吸附机理进行了研究。实验结果：SC中巯基含量大于2％时，每公斤SC对金属离子的吸附容量大于0．2mol；处理水中镉、铅、铜、汞浓度低于0．05mg／L；SC再生后可循环使用。     

Treatment of sugi （Cryptomeria japonica D.） sapwood with aqueous solution of acetic acid

Sugi sapwood samples were processed with aqueous solution of acetic acid in order to find the response of the weight of sugi sapwood and the treatment of aqueous solution of acetic acid. The result showed that loss of weight for the treated sugisapwood was about equal to yield of extracts from sugi sapwood, and increased with the increment of the concentration of aqueous solution of acetic acid. Fourier transform infrared spectroscopy spectra changes of the treated sugi wood and extracts from sugi sapwood were analyzed by FT-IR spectroscopic technique. Increasing tendency of absorption intensities of the stretching vibration at 3 400 cm^-1 of hydroxyl group (OH) and C=C in lignin stretching vibration at 1510 cm^-1 of benzene ring inlignin were observed from FT-IR of the treated sugi sapwood. From FT-IR spectra of extracts from sugi sapwood by aqueoussolution of acetic acid, the dissolution of lignin was observed during the treatment with 30% acetic acid solution aqueous.     

PRELIMINARY STUDY ON MAKING OF WATER RESISTANCE WOOD FIBERBOARD

In the present study,described that preparation of oligoesterified wood fibre by theaddition reaction of the wood fibre with maleic anhydride(MA)and allyl glycidyl ether(AGE).Further,made of crosslinkable oligoesterified fiber board at high temperature and underhigh pressues,accompanying plasticization of the wood fibre components.The product exhibitedthe high the modulus of repture in bending(MOR),good water repellency and dimesionalstability.     

Acetic acid fermentability with <Emphasis Type="Italic">Clostridium thermoaceticum</Emphasis> and <Emphasis Type="Italic">Clostridium thermocellum</Emphasis> of standard compounds found in beech wood as produced in hot-compressed water

Acetic acid fermentability of various compounds from beech wood as produced in a two-step hot-compressed water treatment was evaluated by fermentation tests using standard compounds with Clostridium thermoaceticum and Clostridium thermocellum. For cellulose- and hemicellulose-derived products, the former microorganism was found to ferment compounds with low molecular weights such as monosaccharides, decomposed products, and organic acids to acetic acid, while the latter was found to ferment compounds with high molecular weights such as polysaccharides and oligosaccharides to acetic acid. Lignin-derived products were, on the other hand, fermented by both microorganisms to acetic acid. Based on these lines of evidence, co-culture with C. thermoaceticum and C. thermocellum was evaluated and proven to increase acetic acid fermentability. Consequently, almost all compounds produced from beech wood in hot-compressed water were found to be converted to acetic acid when using these microorganisms in combination. Thus, hot-compressed water treatment coupled with acetic acid fermentation would likely be a powerful method to produce acetic acid from lignocellulosics.