低分子量酚醛树脂处理对杉木细胞壁的改性机理研究

木材细胞壁的改性机理研究是改良木材处理试剂,优化木材处理工艺,提高木材密度、力学、尺寸稳定性等各项性能的关键。以人工林杉木为研究对象,采用合成的水溶性低分子量酚醛树脂(PF)对杉木试材进行逐步的真空加压浸渍处理,通过高精度、高分辨的X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)和核磁共振仪(NMR)(采用交叉极化/魔角旋转法进行连续测试)对处理和对照试样的相关物理和化学性能进行了对比分析,研究结果表明：水溶性低分子量PF处理后,试样的结晶度与未处理的对照样相比,数值降低明显,平均降低率分别为12.67%,11.91%和6.26%。结合FTIR和NMR 13C的检测谱图发现,水溶性低分子量PF改性后的杉木与对照杉木相比,没有增加新的酯类、醚类等官能团特征峰和化学位移,认为水溶性低分子量PF不能与杉木发生明显的化学反应,但会进入到结构较松散、空隙尺寸较大、相对面积较多的管胞细胞壁中的非结晶区,形成物理性的充填,最终引起杉木相对结晶度的降低。本研究对于研发新型木材改性试剂、优化木材改性处理工艺具有重要的参考价值,研究结果还将为进一步探明木材细胞壁的改性机制、丰富木材细胞壁的改性理论提供重要的依据。     

Microdistribution of copper-carbonate and iron oxide nanoparticles in treated wood

Aqueous dispersions of copper-carbonate nanoparticles and microparticles have just begun to be exploited commercially for the preservative treatment of wood. The success of the new systems will depend, in part, on the uniform distribution of the preservative in wood and the ability of copper to penetrate cell walls. We examined the distribution of copper in wood treated with a nano-Cu preservative. Copper particles are not uniformly distributed in treated wood, but they accumulate in voids that act as the flow paths for liquids in wood. Particles are deposited on, but not within cell walls. Nevertheless, elemental copper is present within cell walls, but at a lower level than that in wood treated with a conventional wood preservative. These findings suggest that nano-Cu preservatives are able to deliver bioactive components into wood cell walls even though the majority of copper particles are too large to penetrate the cell wall’s nanocapillary network.     

人工降解饱水木材制备方法与光谱研究

考古出土/出水的饱水木质文物保存状态千差万别,内部降解不均匀、差异大,又有取样的限制,造成许多必需的材性定性定量分析和保护效果评价测试难以进行,因此亟需开发实验室可控制备的人工降解饱水木材技术,以获取大量重复性好、性质均匀的样品供研究使用。以健康黄松为原料,探索使用NaOH-真空浸渍-高压水热的联用法制备人工降解饱水木材,取得了初步的成功。制备的人工降解饱水木材的最大含水率（MWC）为260%,340%和575%,分别达到国际上普遍认定的低、中、高度降解饱水考古木材的MWC水平。红外光谱（FTIR）显示制备的人工降解饱水木材纤维素结构保存较为完好,氢键部分断裂;半纤维素显著降解,主链、侧链有断裂现象,1 732 cm-1特征峰消失;木质素有部分降解,1 508 cm-1处木质素芳香环骨架振动等吸收峰相对强度降低并发生偏移。近红外反射光谱（NIR）显示,制得的样品的三大素均发生降解,半纤维素降解程度最高,木质素次之,木质素相对含量升高,表现为C═O相对含量增加。在1 536～1 580 nm区域形成宽峰且峰强度降低,表明纤维素结晶区分子内部、分子间氢键结构均发生断裂。NaOH-真空浸渍-水热联用法与国际上现用的常压高浓度NaOH浸渍法相比,所需NaOH溶液浓度从50%以上降低到1%、处理时间从数月缩短至10 h,制备效率大大提升,所制得的饱水木材的最大含水率显著增大,与考古木材相近,细胞壁化学结构降解程度显著增大。NaOH-真空浸渍-水热联用法有望实现在实验室可控、快速、大量制备不同降解程度的人工降解饱水木材,对饱水木质文物保护水平的提高具有一定的促进意义。     

Microscopic characterization of tension wood cell walls of Japanese beech (Fagus crenata) treated with ionic liquids

Tension wood that is an abnormal part formed in angiosperms has been barely used for wood industry. In this study, to utilize the tension wood effectively by means of liquefaction using ionic liquid, we performed morphological and topochemical determination of the changes in tension wood of Japanese beech (Fagus crenata) during ionic liquid treatment at the cellular level using light microscopy, scanning electron microscopy and confocal Raman microscopy. Ionic liquid treatment induced cell wall swelling in tension wood. Changes in the tissue morphology treated with ionic liquids were different between normal wood and tension wood, moreover the types of ionic liquids. The ionic liquid 1-ethyl-3-methylimidazolium chloride liquefied gelatinous layers rapidly, whereas 1-ethylpyridinium bromide liquefied slowly but delignified selectively. These novel insights into the deconstruction behavior of tension wood cell walls during ionic liquid treatment provide better understanding of the liquefaction mechanism. The obtained knowledge will contribute to development of an effective chemical processing of tension wood using ionic liquids and lead to efficient use of wood resources.     

Moisture Absorption Behavior of Wood/Plastic Composites Made with Ultrasound-Assisted Alkali-Treated Wood Particulates

The combined effects of alkali and ultrasound treatment of wood flour on the moisture absorption behavior of polypropylene-based wood/plastic composites (WPCs) were examined. FT-IR measurements confirmed that the alkali treatment removed both hemicellulose and lignin from the wood, and there was an increase in the number of hydroxyl groups on the cellulose surface. This process was promoted by ultrasound treatment. Particle size analysis of treated wood fibers revealed that alkali treatment reduced the particle size slightly, and the particle size was further reduced by the assistance of ultrasound. Moisture absorption measurements revealed the interplay between the presence of relative amounts of cellulose, hemicellulose and lignin in the wood and the amount of coupling agent added. It was found that appropriate alkali treatment and an optimum amount of added coupling agent could simultaneously improve composite mechanical properties and reduce both the rate and the maximum amount of moisture absorbed. Further improvements require preferential removal of hemicellulose from the wood and conditions that promote covalent bonding between the coupling agent and the wood reinforcement.     

碱木素的近红外光谱吸收机理的研究

通过碱木素模型物对醌、邻醌和香兰素的溶液在800～900 nm的近红外光谱波段内的吸收谱图的对比发现,对醌和邻醌在此波段产生较强的吸收,而香兰素基本上没有吸收,证明了碱木素的醌型结构在800～900 nm波段内产生特征吸收。对银杏和夹竹桃磨木木素碱处理前后的溶液在800～900 nm波段内的吸光度的差别分析,发现夹竹桃的磨木木素的吸光度的相对变化更大,这是由于夹竹桃磨木木素经碱处理后产生了更多的醌型结构。这也是在硫酸盐法蒸煮过程中在800～900 nm波段内阔叶材的蒸煮液吸光度大于针叶材的蒸煮液吸光度的主要原因。     

Fabrication and Flexural Properties of Bagasse Fiber Reinforced Biodegradable Composites

Biodegradable composites made from bagasse fiber and biodegradable resin were fabricated and the flexural properties of the composites investigated in terms of the effects of fiber length, fiber volume fraction, and different alkali treatments of the bagasse fibers. The flexural properties of the composites increased with the increase in fiber length but decreased below the critical fiber length. The flexural properties increased with the increase in fiber volume fraction. The scanning electron microscope (SEM) micrographs showed that compression of the cellulose structure of bagasse fiber after preparation could have caused enhancement in the flexural properties. Furthermore, when comparing the effects of different alkali treatments of the bagasse fibers, maximum improvement in the flexural properties was observed for the 1% NaOH solution treated fiber composites. After alkali treatment, fibrillation occurred and the surface of the treated fibers became finer; this could contribute to improvement in the fiber‐matrix adhesion and result in enhancing the flexural properties.     

共聚焦显微拉曼光谱研究碱处理对稻秸发酵制沼气的影响

碱水解法以其方便高效成为稻秸发酵制沼气中广泛采用的化学预处理方法,但是碱水解对于稻秸细胞壁中高聚物成分及其空间致密交联结构的作用机理有待深入研究。采用共聚焦显微拉曼光谱和透射电镜研究了NaOH碱处理对稻秸厌氧发酵产沼气的影响。首先对未处理稻秸和碱处理稻秸进行微米级空间分辨率的拉曼光谱面扫描,然后对这两类样本进行主成分分析,发现累计贡献率达99%的前两个主成分空间中两类样本分别呈射线状分布,两类样本分界线清楚表明碱处理导致稻叶组织的拉曼光谱响应特性发生了明显变化;进一步分析前两个主成分的载荷图,发现拉曼峰1 739,1 508和1 094 cm-1是影响主成分的重要谱带,而这三个拉曼峰分别归属于半纤维素、木质素和纤维素的拉曼散射效应;结合半纤维素、木质素和纤维素的拉曼特征峰和显微图像信息实现了组织细胞中三种成分的化学成像分析,发现碱处理破坏了稻叶组织中上述三种成分的致密空间结构,并使它们的含量明显减少,尤其是木质素。由此得出结论：共聚焦显微拉曼光谱可实现稻叶组织细胞中半纤维素、木质素和纤维素的无损检测,结合显微空间信息可实现稻秸中三种成分的化学成像分析,该研究有助揭示碱处理促进秸秆厌氧发酵产沼气的作用机理。     

Effect of Alkali Treatment on Structure and Mechanical Properties of Acrylonitrile–Butadiene–Styrene/Bamboo Fiber Composites

The preparation and properties of wood–plastic composites (WPCs) based on acrylonitrile–butadiene–styrene (ABS) and bamboo fibers (BFs) are described. The BFs were first modified by alkali treatment in order to improve their adhesion to an ABS matrix. The BF modifications were monitored by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Styrene–maleic anhydride (SMA) copolymer, as a compatibilizer, was added to both the untreated and alkali-treated composites. The changes in the structure and the properties resulting from these treatments were observed by the SEM and mechanical tests. The experimental results indicated that both the alkali treatment of the BF and the inclusion of the SMA copolymer improved the interactions between the BF and ABS matrix, and promoted better mechanical properties of the composites.     

Ultrasound-Assisted Surface-Modification of Wood Particulates for Improved Wood/Plastic Composites

The combined effects of alkali and ultrasound treatment of wood flour on the mechanical properties of polypropylene-based wood/plastic composites (WPCs) were examined. FT-IR measurements confirmed that the alkali treatment removed both hemicellulose and lignin from the wood, and there was an increase in the number of hydroxyl groups on the cellulose surface. This process was promoted by ultrasound treatment. Mechanical testing of injection-molded WPC samples revealed that alkali treatment improved both composite strength and modulus when polypropylene grafted with maleic acid was used as a coupling agent. The strength increase is due to improved adhesion between the fiber and matrix, while improved modulus is due to the removal of lignin and hemicellulose that are not as stiff as cellulose. Polarized optical microscopy showed the presence of well-defined polymer crystals on the surface of the modified wood, and this is also responsible for the improved mechanical properties. It is conclusively demonstrated that the combination of chemical treatment of wood and ultrasound assistance is more effective in improving the mechanical properties of the composites than the use of chemical treatment alone.     

真空热处理人工林落叶松木材吸湿性变化机理研究

热处理是一种环境友好型的木材改性方法,可提高木材的耐腐性和尺寸稳定性。研究以落叶松木材为试验材料,在处理温度200 ℃的条件下,对其进行了不同时间的真空热处理。利用动态水蒸气吸附(DVS)对热处理前后木材吸湿性的变化进行了表征,通过傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)和X射线衍射(XRD)分析了热处理前后木材化学组分和结构变化,通过化学变化分析阐明了热处理木材吸湿性变化的作用机制。结果表明：真空热处理落叶松木材的平衡含水率降低,热处理木材的平衡含水率随热处理时间的延长呈逐渐下降的趋势。结合红外光谱和光电子能谱发现,热处理后木材纤维素和半纤维素等化学成分发生降解,木质素发生交联缩合反应,使得吸湿性基团含量减少,碳元素与氧元素含量发生变化,氧碳比降低,从C原子的结合形式来看,热处理材的C1含量增加,C2和C3含量降低,这些化学变化使得热处理材的吸湿性降低。此外,真空热处理未破坏木材的结晶结构,木材的相对结晶度随真空热处理时间的延长而增大,结晶度的增大减少了纤维素分子链上吸水性基团的数量,从而降低了木材的吸湿性。     

Visualising impregnated chitosan in Pinus radiata early wood cells using light and scanning electron microscopy

Chitosan, a deacetylated product of an abundant naturally occurring biopolymer chitin, has been used in a range of applications, particularly in food and health areas, as an antimicrobial agent. In the work reported here Pinus radiata wood was impregnated with chitosan as an environmentally compatible organic biocide (Eikenes et al., 2005a, Eikenes et al., 2005b) to protect wood against wood deteriorating microorganisms and to thus prolong the service life of wooden products. We developed sample preparation techniques targeted to visualise impregnated chitosan within wood tissues using light microscope and field-emission scanning electron microscope (FE-SEM). Sections were viewed with the light microscope without staining with a dye as well as after staining with the dye toluidine blue. Light microscopy was also undertaken on sections that had been stained with 1% aqueous osmium tetroxide (OsO₄). For SEM observations, the sections were treated with OsO₄ and then examined with the FE-SEM, first in the secondary electron imaging mode (SEI) and then in the backscattered electron imaging (BEI) mode, imaging the same areas of a section in both SEI and BEI modes. The preparation techniques employed and the combined use of light and scanning electron microscopy provided valuable complementary information, revealing that chitosan had penetrated into the cavities (cell lumens, intercellular spaces) of all sizes present within wood tissues and had also impregnated early wood cell walls. The information obtained is discussed in relation to its importance in further development of chitosan formulations and refinement of impregnation technologies to optimise chitosan impregnation into and distribution within wood tissues as well as in assessing chitosan efficacy.     

红外光谱法测定杉木/聚丙烯复合材料中木粉和塑料含量

木塑复合材料(wood plastic composites, WPCs)中木材和塑料的配比影响其性能和价格,传统的热化学方法尚不能快速准确地测定WPCs中木塑配比。为探究红外光谱法定量分析WPCs中木粉和塑料的可行性,以杉木、聚丙烯(PP)以及各种添加剂为原料,经过木粉改性、混料和挤出造粒制备出13种不同杉木含量(9.8%～61.5%)的WPCs。采用KBr压片法对制得的样品进行红外光谱分析,通过对比WPCs、杉木、PP以及其他添加剂的红外谱图,确定杉木特征吸收峰为1 059,1 033和1 740 cm-1,1 377,2 839和841 cm-1表征PP特征峰。建立木粉含量、PP含量和二者特征吸收峰峰高比之间的相关关系,结果表明,木粉含量与I_{1 059}/I_{1 377}和I_{1 033}/I_{1 377}之间均存在极强的线性相关,R2分别为0.992和0.993,PP含量与I_{1 377}/I_{1 740}和I_{2 839}/I_{1 740}之间存在高度线性相关,R2分别为0.985和0.981,形成了杉木/PP复合材料中木粉和PP含量的红外光谱定量分析方法,木粉含量预测方程依次为y=53.297x-9.107和y=55.922x-10.238,PP含量预测方程依次为y=6.828 5x+5.403 6和y=8.719 7x+3.295 8。方法精密性和准确性检验表明,方法可重复性强、准确度高,木粉与塑料含量预测平均相对误差约为5%,与传统热化学方法相比,预测精度有较大提高,更重要的是红外光谱法操作更为简便。该研究为杉木/PP复合材料中木粉及塑料含量的测定提供了一种简便、快速、准确的方法。     

Influence of ultrasound pretreatment on wood physiochemical structure

As an initial step to increase the use of renewable biomass resources, this study was aimed at investigating the effects of ultrasound pretreatment on structural changes of wood. Samples were pretreated by ultrasound with the power of 300 W and frequency of 28 kHz in aqueous soda solution, aqueous acetic acid, or distilled water, then pretreated and control samples were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The results shown that ultrasound pretreatment is indeed effective in modifying the physiochemical structure of eucalyptus wood; the pretreatment decreased the quantity of alkali metals (e.g., potassium, calcium and magnesium) in the resulting material. Compared to the control group, the residual char content of samples pretreated in aqueous soda solution increased by 10.08%–20.12% and the reaction temperature decreased from 361 °C to 341 °C, however, in samples pretreated by ultrasound in acetic solution or distilled water, the residual char content decreased by 12.40%–21.45% and there were no significant differences in reactivity apart from a slightly higher maximum reaction rate. Ultrasound pretreatment increased the samples’ crystallinity up to 35.5% and successfully removed cellulose, hemicellulose, and lignin from the samples; the pretreatment also increased the exposure of the sample to the treatment solutions, broke down sample pits, and generated collapses and microchannels on sample pits, and removed attachments in the samples.     

Qualitative and quantitative assessment of extracted oil from Camelina sativa seed treated by dielectric-barrier discharge cold plasma

This study aimed to investigate the effects of dielectric-barrier discharge (DBD) cold plasma (CP) pretreatment on Camelina sativa “Soheil cultivar” seed. A DBD plasma reactor system was employed for this purpose. The experiments were performed by taking into account variables including voltages of 15, 18, and 21 kV and times of 2, 4, 8, and 16 min. The measured properties were oil yield extraction (%), oil colour parameters (CIEL*a*b*), protein content (meal) (%), surface analysis using Scanning Electron Microscopy (SEM), and fatty acids profile of Camelina sativa. The results revealed that the CP treatment had a significant improvement in different properties of the extracted oil. It was observed that the extracted oil was increased, with the increasing time of CP exposure. The treatments of CP enhanced the oil yield from 24.3 to 31.5%, and the optimal conditions were identified as 21 kV and 16 min. Also, the maximum protein amount was observed for the samples treated by CP (39.5%). The SEM analysis showed that the cell structures of pre-treated Camelina samples were damaged, thereby improved the oil extraction efficiency. The variations in the values of L*, a*, and b* (max-min) were calculated to be 3.9, −2.5, and 9.7, respectively, which indicated minor changes of CP treatment on the oil colour parameters. The treated samples showed considerable changes of enhancement in linolenic and linoleic acids among poly-unsaturated fatty acids; and a reduction in palmitic acid content, among saturated fatty acids.     

Intensification of alkaline delignification of sugarcane bagasse using ultrasound assisted approach

Ultrasound-assisted approach has been investigated for delignification so as to develop green and sustainable technology. Combination of NaOH with ultrasound has been applied with detailed study into effect of various parameters such as time (operating range of 15–90 min), alkali concentration (0.25 M−2.5 M), solvent loading (1:15–1:30 w/v), temperature (50–90 ˚C), power (40–140 W) and duty cycle (40–70 %) at fixed frequency of 20 kHz. The optimized operating conditions established for the ultrasonic horn were 1 M as the NaOH concentration, 1 h as treatment time, 70˚C as the operating temperature, 1:20 as the biomass loading ratio, 100 W as the ultrasonic power and 70% duty cycle yielding 67.30% as the delignification extent. Comparative study performed using conventional and ultrasonic bath assisted alkaline treatment revealed lower delignification as 48.09% and 61.55% respectively. The biomass samples were characterized by SEM, XRD, FTIR and BET techniques to establish the role of ultrasound during the treatment. The morphological changes based on the ultrasound treatment demonstrated by SEM were favorable for enhanced delignification and also the crystallinity index was more in the case of ultrasound treated material than that obtained by conventional method. Specific surface area and pore size determinations based on BET analysis also confirmed beneficial role of ultrasound. The overall results clearly demonstrated the intensification obtained due to the use of ultrasonic reactors.     

XRF spectrometer calibration for copper determination in wood

Method of X‐ray fluorescence (XRF) spectrometer calibration for copper analysis in wood was elaborated. Copper salt standard solutions for XRF measurements of liquid samples were prepared, and calibration curve of copper content dependence on impulse counts was determined. Specimens of pine wood (Pinus sylvestris L.) were treated with different solutions of copper‐based preservative (alkaline copper quarternary ammonium compound type) applying model low‐pressure preservation process. After treatment, wood specimens were sliced into six pieces, and exposed surfaces were analyzed using mapping option of XRF spectrometer. Then, wood from each analyzed surface was peeled with abrasive paper and dissolved in 65% nitric (V) acid. Copper content in solutions was determined using obtained calibration curve, and calibration dependence of copper content in wood on the average impulse counts on particular surfaces was calculated. Obtained results of copper content were consistent with values calculated on the basis of differences of samples weight before and after treatment. It confirms that proposed procedure is correct, and obtained equation may be used for unknown samples examination. Copyright © 2012 John Wiley & Sons, Ltd.     

ICP—AES法同时测定硼铁中的主要成分及杂质

本文研究了用ＩＣＰ－ＡＥＳ法同时测定硼铁中的主要成分Ｂ、Ｆｅ及杂质元素、Ａｌ、Ｍｎ，Ｓｉ的方法。采用碱熔融法分解样品，选Ｃｄ作为内标元素。     

Improving the bioactivity of NiTi shape memory alloy by heat and alkali treatment

TiO₂ films were formed on an NiTi alloy surface by heat treatment in air at 600 °C. Heat treated NiTi shape memory alloys were subsequently alkali treated with 1 M, 3 M and 5 M NaOH solutions respectively, to improve their bioactivity. Then treated NiTi samples were soaked in 1.5SBF to evaluate their in vitro performance. The results showed that the 3 M NaOH treatment is the most appropriate method. A large amount of apatite formed within 1 day's soaking in 1.5SBF, after 7 day's soaking TiO₂/HA composite layer formed on the NiTi surface. SEM, XRD, FT-IR and TEM results showed that the morphology and microstructure are similar to the human bone apatite.     

基于共聚焦显微拉曼光谱揭示炭疽病侵染下茶叶细胞壁变化的研究

采用共聚焦显微拉曼技术研究了炭疽病感染所致茶叶细胞壁结构和化学成分的变化。对茶叶健康和染病组织细胞进行微米级空间分辨率的显微拉曼光谱扫描,并结合透射电镜观察炭疽病侵染所致的细胞超微结构变化,结果显示染病前后细胞壁的拉曼光谱位移和强度都有明显的差异,表明炭疽病侵染导致细胞壁中化学成分发生了较大的变化。其中由纤维素,果胶,酯类化合物产生的拉曼峰强度都有明显下降,说明细胞壁中这些物质的含量在染病后减少了;而木质素拉曼散射引起的拉曼峰强度有所上升,说明木质素的含量在染病后有所增加。随后基于纤维素的拉曼指纹波数和显微空间结构信息实现了茶叶健康组织和染病组织细胞壁中纤维素的化学成像分析,结果显示炭疽病侵染不仅导致细胞壁中纤维素的含量大大减少,而且纤维素的有序结构被破坏。由此得出结论：在无需对样本进行染色或复杂的化学处理的情况下,共聚焦显微拉曼可以揭示由炭疽病侵染引起的茶叶细胞壁化学成分和结构的变化,本研究是共聚焦显微拉曼技术首次用于植物病理学中寄主-病原物互作机制的研究,将为深入研究寄主-病原物在细胞层面上的互作机制开辟蹊径。