利用核磁共振测定木材吸着水饱和含量

利用核磁共振(NMR)技术研究了室温与-3 ℃ 条件下 5 种树种木材内水分质子的自旋-自旋弛豫时间(T₂)特性,室温下各树种木材试样 T₂ 弛豫时间特性的不同是由木材微观构造导致的．通过对比冷冻前后各树种试样的信号反演峰面积,确定了其吸着水饱和含量,樟子松 38.3%,杉木 38.5%,杨木 36.0%,白蜡木 35.6%,轻木 47.6%,均高于通过吸湿外推法估算数值,与溶剂排出法、多孔板法、离心法等实测法获得的吸着水饱和含量的结果相近,核磁共振技术可作为木材内吸着水含量快速测定的实验方法．
     

利用TD-NMR技术研究杨木高温干燥过程水分分布

木材中水分状态变化和迁移对木材的物理性质有重要影响.通过时域核磁共振技术(TD-NMR)可以从分子层面解读木材与水分的关系,可以为木材干燥、木制品加工提供理论依据和实践参考.该研究以北京杨为研究对象,通过对高温干燥过程中木材内部水分变化的自由感应衰减(FID)曲线和横向弛豫时间(T_2)进行测定与分析,探究木材干燥过程中水分状态变化及迁移过程.研究结果表明,FID和T_2信号量与木材含水率高度线性相关,由此可以计算木材在干燥过程中任意时刻的含水率.通过对干燥过程中水分T_2分布的分析表明:心材试件在干燥过程中,长弛豫时间自由水(c状态水分)的拟合面积出现了先减小后增大然后再减小的趋势,而边材试件中则不存在这种现象.在北京杨心材试件中含量最多的是弛豫时间为10 ms数量级的水分,而在边材试件中各状态水分含量差异较小,含量最多的是弛豫时间为100 ms数量级的水分.在高温干燥过程中,边材试件内各状态水分百分含量减少的速度快于心材,各试件中自由水的蒸发速度明显快于结合水.     

人造板吸水过程的 TD-NMR 动态研究

利用时域核磁共振(TD-NMR)技术,为研究人造板和水分的关系提供新方法．该文通过研究胶合板(Plywood)、刨花板(Particle board)、中密度纤维板(Medium Density Fiberboard) 3 种常用人造板吸水过程中水分的自由感应衰减(FID)信号的变化,得出传统称重法得到的吸水率与吸水过程中测得的 FID 信号高度线性相关, 24 h 吸水率由大到小依次为胶合板>刨花板>中密度纤维板．通过 3 种人造板 24 h 吸水过程中自旋-自旋弛豫时间(T₂)大小及分布的实验数据,分析了吸水过程中人造板中水分的状态．实验结果证实了TD-NMR 是研究人造板与水分的关系的一个有效手段．
     

浮压下马尾松的干燥特性及水分迁移机理初探

本文阐述了马尾松在浮压真空条件下的干燥特性．实验结果显示,浮压干燥比常压干燥能明显加快木材内水分迁移的速率,特别是在低含水率阶段（纤维饱和点以下）更明显．文中还对浮压条件下细胞壁内吸着水的迁移机理进行了初步的探讨分析．     

利用地球磁场测量质子的自旋弛豫时间

利用地球磁场核磁共振(EF NMR)的方法测量水中质子自旋弛豫的时间.两种不同的自旋弛豫时间T_1和T_2分别测得为(2.46±0.16)s和(0.83±0.02)s,与《Measurement Science and Technology》2012年(21卷)第10期上Michal CA一文所得到的结果T_1=2.3±0.1 s吻合较好.此外,实验数据也验证了居里定律,并通过对硫酸铜溶液的测量说明了溶液中离子的存在会使自旋弛豫过程加快.此工作提供了一种利用地球磁场测量秒量级的自旋弛豫时间的方法.     

原位聚合制备木材/羟甲基脲复合材料及其表征

以杨木生材为原料,采用原位聚合方法制备木材/羟甲基脲复合材料.羟甲基脲在脉冲式压力的作用下浸渍到木材内,在热压干燥过程中,经过原位聚合制备木基复合材料.根据国标对改性前后的木材化学成分进行了分析,并利用X射线光电子能谱(XPS)、核磁共振分析(3C-NMR)、EDXA对改性前后木材中碳和氮元素含量、分布以及官能团变化进...     

单层GaSe表面Fe原子吸附体系电子自旋性质调控

Ⅲ族金属单硫化物因其优越的光电和自旋电子特性而备受关注,实现对其自旋性质的有效调控是发展器件应用的关键.本文采用密度泛函理论系统地研究了GaSe表面Fe原子吸附体系的几何构型及自旋电子特性.Fe/GaSe体系中Fe吸附原子与最近邻Ga,Se原子存在较强的轨道耦合效应,使体系呈现100%自旋极化的半金属性.其自旋极化贡献主要来源于Fe-3d电子的转移及Fe-3d,Se-4p和Ga-4p轨道杂化效应.对于Fe双原子吸附体系,两Fe原子之间的自旋局域导致原本从Fe转移至GaSe的自旋极化电荷量减少,从而费米能级附近的单自旋通道转变为双自旋通道,费米能级处的自旋极化率转变为0.研究结果揭示了Fe_n/GaSe吸附体系自旋极化特性的形成和转变机制,可为未来二维自旋纳米器件的设计与构建提供参考.     

储油岩芯二相液体吸附特性的NMR研究及应用

为研究储油岩芯对液体的吸附机理,我们特地用同一岩芯制成以下几种样品:(1)吸附不同量的煤油;(2)吸附不同量的水;(3)先吸附一定量的水再吸附一定量的煤油.对以上三组样品,做了NMR自旋—晶格弛豫时间测定;考查了岩芯样品中各弛豫成分量与液体吸附量的变化规律;得出了岩芯内水和煤油受束缚越紧其弛豫时间越短的结论.并依据大量石油地质学的结论建立了砂岩孔隙中油水二相系统的核磁共振模型.     

以双量子谱解析胰岛素类似物中氨基酸残基质子自旋体系

氨基酸残基质子自旋体系解析,是以核磁共振方法研究蛋白质等生物大分子结构、功能、运动的基础。二维双量子谱是解析残基质子自旋体系的重要手段。对B链C端去五肽胰岛素及S-磺酸型胰岛素A链,分别在水中及重水中测定其500 MHz相敏双量子谱和300 MHz相敏双量子谱。由双量子谱的直接峰、远程峰、等价峰,解析各类残基质子自旋体系,确认了从COSY谱所作的解析,提供了可供解析的更多信息。     

基于多尺度模型预测木材含水率和温度的变化

了解木材干燥过程中的水分迁移和热量传递规律有助于提高木材的干燥质量,改善干燥工艺,节约能源。以樟子松(Pinus sylvestris)为材料,建立能够较准确模拟木材干燥过程中含水率和温度分布变化的多尺度单元表征模型,模型由宏观尺度上三个耦合方程一两个水分扩散方程和一个热量平衡方程,以及微观尺度上的单个细胞水分迁移的平衡方程组成。解析模型的过程为:分析初始条件和边界条件、有限元网格的生成、方程离散化、查找相应物性参数、MATLAB软件编程求解。最后通过实验分析验证了建立的多尺度模型的准确性,进行试件在80℃时各层含水率随时间变化的实验,实验结果与模拟值比较,曲线吻合性较好,多尺度模型可以反映木材干燥过程中含水率的分布。最后对建立的多尺度模型进行理论分析,预测了干燥过程中各层温度的变化和分布,进一步验证模型的准确性。从不同尺度建立的木材热质转移数学模型,能较为准确的反映木材含水率的变化和空间分布情况,为干燥过程水分和温度分布的研究提供了一定的理论基础和参考价值。     

Effect of moisture content on ultrasonic velocity and attenuation in woods

Ultrasonic velocity and attenuation are measured at 1 MHz in several kinds of wood as a function of the moisture content U. The results are interpreted in terms of water absorption mechanism of woods. The velocity decreases rapidly with increasing U up to a critical value U₁ at which the curve shows a sharp bend, and the decrease is very slow for U>U₁. This critical point U₁ is in the range 20–50% depending on the species of wood and is regarded as the fibre saturation point of the wood, the moisture content at which the wood substance is saturated with absorbed water. Ultrasonic measurements thus provide us with an accurate way to determine the fibre saturation point. The attenuation curve also shows a critical change at U = U₂, which is slightly lower than U₁. The attenuation shows no change from U = 0 up to U₂, but begins to increase rapidly thereafter. This point U₂ indicates the moisture content at which free water begins to enter the vacant space of wood cells.     

Fabrication of superhydrophobic wood surfaces via a solution-immersion process

Superhydrophobic wood surfaces were fabricated from potassium methyl siliconate (PMS) through a convenient solution-immersion method. The reaction involves a hydrogen bond assembly and a polycondensation process. The silanol was formed by reacting PMS aqueous solution with CO₂, which was assembled on the wood surface via hydrogen bonds with the wood surface -OH groups. The polymethylsilsesquioxane coating was obtained through the polycondensation reaction of the hydroxyl between wood and silanol. The morphology of products were characterized using a scanning electron microscope (SEM), the surface chemical composition was determined using energy dispersive X-ray analysis (EDXA), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TGA) and contact angle measurement. Analytical results revealed that rough protuberances uniformly covered the wood surface, thus transforming the wood surface from hydrophilic to superhydrophobic. The water contact angle of the superhydrophobic wood surface was about 153° and a sliding angle was 4.6°.     

Microstructural features assessment of different waterlogged wood species by NMR diffusion validated with complementary techniques

Wood is a hygroscopic, multi-scale and anisotropic natural material composed of pores with different size and differently oriented. In particular, archaeologically excavated wood generally is waterlogged wood with very high moisture content (400%–800%) that need to have a rapid investigation at the microstructural level to obtain the best treatment with preservative agents. Time-dependent diffusion coefficient D(t) quantified by Pulse Field Gradient (PFG) Nuclear Magnetic Resonance (NMR) techniques provides useful information about complex porous media, such as the tortuosity (τ) describing pore connectivity and fluid transport through media, the average-pore size, the anisotropic degree (a_n). However, diffusion NMR is intrinsically limited since it is an indirect measure of medium microstructure and relies on inferences from models and estimation of relevant diffusion parameters. Therefore, it is necessary to validate the information obtained from NMR diffusion parameters through complementary investigations. In this work, the structures of five waterlogged wood species were studied by PFG of absorbed water. D(t) and τ of water diffusing along and perpendicular to vessels/tracheids main axes together with relaxation times and a_n were quantified. From these parameters, the pore sizes distribution and the wood microstructure characterization were obtained. Results among wood species were compared, validated and integrated by micro-imaging NMR (μ-MRI), environmental-scanning electron-microscope (ESEM) images, wood dry density and imbibition times measurement of all woods. The work suggests that a_n vs τ rather than the estimated pore size diversifies and characterize the different wood species. As a consequence diffusion-anisotropy vs tortuosity could be an alternative method to characterize and differentiate wood species of waterlogged wood when high resolution images (μ-MRI and ESEM) are not available. Moreover, the combined use of D(t) and micro-MRI expands the scale of dimensions observable by NMR covering all the interesting length scales of wood.     

Inorganic UV absorbers for the photostabilisation of wood-clearcoating systems: Comparison with organic UV absorbers

Inorganic UV absorbers which are widely used today were originally designed neither as a UV blocker in coatings applications, nor for wood protection. In recent years however, there has been extensive interest in these compounds, especially with regard to their properties as a UV blocker in coating applications.In this work, we carried out a comparative study to look into some inorganic and organic UV absorbers used in wood coating applications. The aim of this study is to determine the photostabilisation performances of each type of UV absorbers, to seek possible synergies and the influences of different wood species. We have also searched to find eventual correlation between these performances and the influence of UV absorbers on the film properties. Our study has compared the performances of the following UV absorbers: hombitec RM 300, hombitec RM 400 from the Sachtleben Company; transparent yellow and red iron oxides from Sayerlack as inorganic UV absorbers; organic UV absorbers Tinuvin 1130 and Tinuvin 5151 from Ciba Company.The study was carried out on three wood species: Abies grandis, tauari and European oak.The environmental constraints (in particular the limitation of the emission of volatile organic compounds VOCs) directed our choice towards aqueous formulations marketed by the Sayerlack Arch Coatings Company.The results obtained after 800 h of dry ageing showed that the Tinuvins and the hombitecs present better wood photostabilisations.On the other hand in wet ageing, with the hombitec, there are appearances of some cracks and an increase in the roughness of the surface. This phenomenon is absent when the Tinuvins are used. With regard to these results, the thermomechanical analyses relating to the follow-up of the change of the glass transition temperature (T_g) of the various coating systems, show a different behaviour between the two types of absorbers. However, contrary to organic UV absorbers, inorganic ones tend to increase T_g during ageing, and, consequently decrease the flexibility of films. These phenomena can lead to the appearance of cracks found in the case of the wet weathering.     

Spectroscopic studies of electronic structure of copper(II) ethanolamine complexes in solutions and in impregnated wood

Optical and electron paramagnetic resonance (EPR) spectra were recorded for a series of Cu(II) complexes with monoethanolamine (EA) and the quaternary ammonium compound (QAC) alkyldimethylbenzylammonium chloride in aqueous solution with H₃BO₃ which are tested as modern impregnating solutions for wood preservation. It is proved that in aqueous solutions of Cu-EA the octahedral complexes I, Cu(EA)₂(H₂O)₂, exist with water in apical positions. The addition of the QAC results in an exchange of water for nitrogen of the QAC molecules with a possible partial destruction of the coordinating molecule (complex II). The detailed electronic structure is determined for both species I and II. Boric acid does not influence the complex structures. In the treated wood (Pinus silvestris L.) the complex I is destroyed and Cu(EA)₂ is attached to the OH groups of cellulose molecules, forming a stable complex. The complexes II still exist in wood, but with higher-concentration impregnating solution a part of these complexes is destroyed by coordination to the OH groups of cellulose molecules.     

Modification of Wood Flour Surfaces by Esterification with Acid Chlorides: Use in HDPE/Wood Flour Composites

Modification of wood fiber/flour (WF) surfaces can improve their compatibility with hydrophobic plastic matrices and reduce composite water uptake. WF was esterified with octanoyl chloride and palmitoyl chloride. Modified WF was analyzed by FT-IR. More extensive esterification occurred in highly polar dimethylformamide (DMF) than in much less polar CHCl₃ or methyl tert-butyl ether (MTBE). DMF penetrates into the fiber far more than CHCl₃ or MTBE, making more –OH groups available for esterification. Increasing the acid chloride chain length from C₈ to C₁₆ decreased the mole fraction of esterification. Longer chains cover surface –OH groups, retarding reactions with nearby hydroxyls after esterification. Longer chain acid chlorides also have lower reactivity and penetrate into the hydrophilic wood fiber more slowly. Modified wood flour surfaces were covered by a hydrophobic layer of ester groups (SEM). Modified wood flour surfaces and WF/HDPE composite fracture surfaces were studied by SEM. C₈-modified wood flour (60 wt%)/HDPE composites exhibited far less water absorption after 24 h and 216 h immersions compared with unmodified WF (60 wt%)/HDPE composites. Water absorption continues over the 216 h period. Esterified WF/HDPE composites exhibited lower flexural strengths and moduli. In contrast to C₈-esterification, the addition of maleated polypropylene (MAPP) to WF/HDPE composites improved composite mechanical performance and gave similar water absorption properties to C₈-esterified WF composites.     

Investigation of radiological properties of some shielding materials on charged and uncharged radiation interaction for neutron generator

Radiation interaction parameters such as total stopping power, projected range (longitudinal and lateral) straggling, mass attenuation coefficient, effective atomic number (Z_eff) and electron density (N_eff) of some shielding materials were investigated for photon and heavy charged particle interactions. The ranges, stragglings and mass attenuation coefficients were calculated for the high-density polyethylene(HDPE), borated polyethylene (BPE), brick (common silica), concrete (regular), wood, water, stainless steel (304), aluminum (alloy 6061-O), lead and bismuth using SRIM Monte Carlo software and WinXCom program. In addition, effective atomic numbers (Z_eff) and electron densities (N_eff) of HDPE, BPE, brick (common silica), concrete (regular), wood, water, stainless steel (304) and aluminum (alloy 6061-O) were calculated in the energy region 10?keV–100?MeV using mass stopping powers and mass attenuation coefficients. Two different methods namely direct and interpolation procedures were used to calculate Z_eff for comparison and significant differences were determined between the methods. Variations of the ranges, longitudinal and lateral stragglings of water, concrete and stainless steel (304) were compared with each other in the continuous kinetic energy region and discussed with respect to their Z_effs. Moreover, energy absorption buildup factors (EABF) and exposure buildup factors (EBF) of the materials were determined for gamma rays as well and were compared with each other for different photon energies and different mfps in the photon energy region 0.015–15?MeV.     

A Review of Infrared Spectra from Wood and Wood Components Following Treatment with Liquid Ammonia and Solvated Electrons in Liquid Ammonia

ABSTRACT

The chemical changes that occur in wood and wood components (cellulose, holocellulose and lignin) following treatment with liquid ammonia and solvated electrons (e^? _s,) in liquid ammonia have been investigated using FTIR spectroscopy.

When ammonia penetrates into a wood structure, all carboxylate groups will react with ammonia to form ammonium salts, aldehydic and ketonic groups will follow a similar reaction to produce imines, and ester groups will react to forni amides.

After treatment with (e^? _s) in liquid ammonia, wood samples show diminished absorption around 15 13 cm^?1, a position corresponding to aromatic groups, and diminished absorption peaks associated with aldehydic, ketonic, and ester groups.

The overall changes in the IR spectra of cellulose in liquid ammonia and (e^? _s) in liquid ammonia are not dramatic. The IR spectra of the isolated holocellulose after treatment with (e^? _s) in liquid ammonia have intensities and band shape similar to those of cellulose. The isolated lignin behaves in a manner similar to wood, in that the liquid ammonia causes some decrease in the intensities of absorptions associated with C-O and C=O bands, and increase in strength of the amide functional group at 1600 cm^?1. The resulting extracts of wood, following treatment with (e^? _s) in liquid ammonia, appear to loose their “aromaticity”.

Because wood has long been used, and still is used extensively as an important constructional material, the changes in mechanical characteristics caused by the action of various reducing agents appears to have been an important area of scientific interest. The following review focuses on the chemical changes in the functional groups of the surface moieties of wood when treated with a reducing agent, such as (e^? _s + NH_3liq), using infrared spectroscopy.     

Effect of extractives on the flexural properties of wood/plastic composites

This study investigated the effect of extractives in wood flour on the mechanical properties of wood-polypropylene (PP) composites. Three different solvents, acetone/water, dioxane/water and benzene/ethanol, were used to remove extractives in both pine and Douglas fir wood flour. X-ray photoelectron spectroscopy (XPS) confirmed that extraction resulted in a change in the surface composition of the wood flour. Differential scanning calorimetry showed no changes in the percent crystallinity of the PP matrix in the wood-PP composites and optical microscopy showed no detectable changes in PP spherulite size or shape between filled PP containing extracted and unextracted wood flour. A large increase in the strength of pine flour-PP composites was observed upon removal of extractives from pine flour. The Douglas fir flour-PP composites showed a smaller, but statistically significant, increase in strength upon removal of extractives, with the exception of the dioxane/water extracted Douglas fir. Significant differences were also observed in stiffness between extracted wood-PP and unextracted wood-PP composites with the exception of the dioxane/water extracted Douglas fir, which was not significantly different from the control.