核磁共振研究木材吸着过程中水分吸附机理

核磁共振方法以质子(H)为探针,为研究木材与水分的关系提供了一个新的视角. 该文通过研究杨木在32 ℃恒温、相对湿度为98%恒湿环境下杨木吸着过程中质子的自旋-自旋弛豫时间T₂的变化,进而来分析木材吸着过程中水分的分布与迁移特性. 探测木材吸着过程中水分的迁移行为,为解释木材与水分的关系提供了一个有力的理论依据,同时从微观层面揭示木材吸着过程中水分的吸附机理,其水分吸附机理同样适用于食品等领域. 实验结果证实核磁共振是揭示木材与水分的复杂关系的一个有效的手段.     

Relative humidity and temperature dependence of mechanical degradation of natural fiber composites

In this paper, the mechanical degradation of natural fiber composites is studied with the consideration of the relative humidity and the temperature. A nonlinear constitutive model is established, which employs an internal variable to describe the mechanical degradation related to the energy dissipation during moisture absorption. The existing experimental researches demonstrated that the mechanical degradation is an irreversible thermodynamic process induced by the degradation of fibers and the damages of interfaces between fiber and matrix, both of which depend on the variation of the relative humidity or the temperature. The evolution of the mechanical degradation is obtained through the determination of dissipation rates as a function of the relative humidity and the temperature. The theoretically predicted mechanical degradations are compared with experimental results of sisal fiber reinforced composites subject to different relative humidity and temperatures, and a good agreement is found.     

温度变化对近红外光谱预测木材含水率的影响

为实现温度不稳定环境下木材含水率的近红外光谱检测,探究了不同温度下木材近红外光谱的变化规律及温度变化对近红外预测木材含水率的影响。对从林场采集的樟子松、水曲柳、大青杨和红松原木木块试样各75块,共计300块试样,进行了不同温度和含水率条件下的近红外光谱采集。采用单一温度下的校正集分别与各个温度下的验证集建立偏最小二乘含水率预测模型,探究温度变化对木材含水率模型预测准确性的影响。比较了不同光谱预处理的木材含水率预测温度全局模型。采集相同含水率下不同温度的近红外光谱数据,对光谱进行光谱平均、一次微分、主成分分析和偏最小二乘判别分析,以探究温度变化时,木材近红外光谱的变化规律。结果显示：（1）温度对木材样品光谱存在显著影响;主成分分析和判别分析表明不同温度下的样品有明显聚类趋势,温度判别准确率为96.1%。温度会影响木材的近红外光谱在特定波长吸收峰的位置及吸光度,在含水率相同的情况下,随着温度的升高,特定位置吸收峰有逐渐向高频波段转移的趋势且在零下低温时波峰移动变化更明显。（2）不同温度下的PLS含水率预测模型对温度变动的适应能力有差异,木材含水率预测模型更适应于检测与建模样本相同温度的样品。与单一温度模型相比,PLS温度全局模型对于温度变化具有很好的适应性和应用潜力,RMSEP低于大部分单一温度模型。基于SG平滑+多元散射校正+一次微分预处理联用的PLS含水率温度全局模型有较好的预测效果和温度适应性,RMSEP降为0.074。可见,温度变动是近红外法检测木材含水率的过程中不可忽视的扰动因素;基于光谱预处理的温度全局模型可以显著提高温度适用性。该研究可进一步促进近红外光谱技术在木材生产、加工过程中的应用。     

Measurement of radiative gas and particle emissions in biomass flames

Radiation is the dominant mode of heat transfer near the burner of coal and biomass-fired boilers. Predicting and measuring heat transfer is critical to the design and operation of new boiler concepts. The individual contributions of gas and particle phases are dependent on gas and particle concentration, particle size, and gas and particle temperature which vary with location relative to the flame. A method for measuring the contributions of both gas and particle radiation capable of being applied in harsh high temperature and pressure environments has been demonstrated using emission from particles and water vapor using an optical fiber probe transmitting a signal to a Fourier Transform Infrared (FTIR) spectrometer. The method was demonstrated in four environments of varying gas and particle loading using natural gas and pulverized wood flames in a down-fired 130?kW_th cylindrical reactor. The method generates a gas and particle temperature, gas concentrations (H₂O and CO₂), total gas and particle intensities, and gas and particle total effective emissivity from line-of-sight emission measurements. For the conditions measured, downstream of the luminous flame zone, water vapor and CO₂ radiation were the dominant modes of heat transfer (effective emissivity 0.13–0.19) with particles making a minor contribution (effective emissivity 0.01–0.02). Within a lean natural gas flame, soot emission was low (effective emissivity 0.02) compared to gas (0.14) but within a luminous flame of burning wood particles (500?µm mean diameter) the particles (soot and burning wood) produced a higher effective emissivity (0.17) than the gas (0.12). The measurement technique was therefore found to be effective for several types of combustion environments.     

Thermal conductivity of high-porosity heavily doped biomorphic silicon carbide prepared from sapele wood biocarbon

The electrical resistivity and thermal conductivity of high-porosity (～52 vol %, channel-type pores) bio-SiC samples prepared from sapele wood biocarbon templates have been measured in the temperature range 5–300 K. An analysis has been made of the obtained results in comparison with the data for bio-SiC samples based on beech and eucalyptus, as well as for polycrystalline β-SiC. The conclusion has been drawn that the electrical resistivity and thermal conductivity of bio-SiC samples based on natural wood are typical of heavily doped polycrystalline β-SiC.     

竹材的纳米TiO_2改性及抗菌防霉性能研究

竹材是一种重要的森林资源,但容易腐朽霉变,在户外使用受到限制。可采用溶胶-凝胶法,在低温条件下制备了TiO2溶胶,并通过浸渍提拉的方式,完成了竹材的纳米TiO2改性。同时利用电子核磁共振波谱仪(NMR)、场发射环境扫描电镜(FESEM)、X射线衍射仪(XRD)、X射线能谱仪(EDAX)对TiO2进行形态和结构表征,重点研究了温度对TiO2薄膜形态、晶型及抗菌防霉性能的影响。研究结果表明,3种温度(20,60,105℃)处理的TiO2改性竹材不仅完全保持了竹材的天然颜色、纹理、结构,而且抗菌性能由不具抗菌性变为对大肠杆菌的杀菌率超过99%,防霉性能提高了10倍以上。这种方法有望成为竹材功能性改良的新手段,并对包括木材在内的其他天然生物质材料保护和改良也具有借鉴意义。     

Comparison of the protection effectiveness of acrylic polyurethane coatings containing bark extracts on three heat-treated North American wood species: Surface degradation

High temperature heat-treatment of wood is a very valuable technique which improves many properties (biological durability, dimensional stability, thermal insulating characteristics) of natural wood. Also, it changes the natural color of wood to a very attractive dark brown color. Unfortunately, this color is not stable if left unprotected in external environment and turns to gray or white depending on the wood species. To overcome this problem, acrylic polyurethane coatings are applied on heat-treated wood to delay surface degradations (color change, loss of gloss, and chemical modifications) during aging. The acrylic polyurethane coatings which have high resistance against aging are further modified by adding bark extracts and/or lignin stabilizer to enhance their effectiveness in preventing the wood aging behavior. The aging characteristic of this coating is compared with acrylic polyurethane combined with commercially available organic UV stabilizers. In this study, their performance on three heat-treated North American wood species (jack pine, quaking aspen and white birch) are compared under accelerated aging conditions. Both the color change data and visual assessment indicate improvement in protective characteristic of acrylic polyurethane when bark extracts and lignin stabilizer are used in place of commercially available UV stabilizer. The results showed that although acrylic polyurethane with bark extracts and lignin stabilizer was more efficient compared to acrylic polyurethane with organic UV stabilizers in protecting heat-treated jack pine, it failed to protect heat-treated aspen and birch effectively after 672 h of accelerated aging. This degradation was not due to the coating adhesion loss or coating degradation during accelerated aging; rather, it was due to the significant degradation of heat-treated aspen and birch surface beneath this coating. The XPS results revealed formation of carbonyl photoproducts after aging on the coated surfaces and chain scission of CN of urethane linkages.     

光纤布拉格光栅嵌入SMS光纤结构的湿度传感器

提出了一种基于光纤布拉格光栅嵌入单模-多模纤芯-单模(single-mode-multimode fiber core-single mode, SMS)光纤结构的湿度传感器。当环境湿度变化时,SMS光纤结构的干涉光谱会发生漂移,而光纤布拉格光栅对湿度不敏感,其纤芯基模保持不变。因此利用SMS光纤结构对环境湿度的敏感性去调制光纤布拉格光栅纤芯基模,通过检测光纤布拉格光栅纤芯基模的反射能量变化就可以实现湿度测量。数值模拟了SMS光纤结构的内部光场分布规律,理论计算了不同环境折射率时,多模纤芯的长度、直径对SMS光纤结构输出能量耦合系数的影响。理论模拟表明,随着环境折射率变化,SMS光纤结构中传输的纤芯基模的输出能量耦合系数会发生变化。同时制作了传感器样品并对其进行了传感实验研究,实验结果表明多模纤芯长35 mm、纤芯直径为85 μm的传感器在45%～95%RH湿度变化范围内,湿度灵敏度为0.06 dBm·(%RH)-1。在20～80 ℃温度范围内,传感器的温度灵敏度为0.008 nm·℃-1,温度所带来的湿度测量误差为0.047%RH·℃-1。传感器具有制作简单、灵敏度高、反射式能量检测等优点,在湿度测量领域有一定的应用价值。     

Mechanical characteristics of aged Hinoki wood from Japanese historical buildings

Wood is present in many cultural heritage objects in Japan thanks to its capacity to resist over a long period of time. However, the evolution of its properties in regular use remains insufficiently known. The present study on the effect of wood aging takes advantage of the Japanese context where building traditions have been maintained for centuries. 3-point bending tests were performed in longitudinal (L) and radial (R) directions on small clear wood specimens cut from 8 historical samples and one modern reference considered of high quality by craftsmen. Although aged wood appeared more rigid and stronger than recent wood, after density and humidity corrections were applied no significant variation of L and R rigidity or L strength was observed. The post-linear behaviour, however, was drastically influenced by wood age especially in R direction where the strength and rupture energy decreased markedly with the time elapsed since the wood was processed. Well preserved aged wood considered as safe as long as it is not loaded perpendicular to grain. To cite this article: M. Yokoyama et al., C. R. Physique 10 (2009).     

基于无线传输的车载温湿度测量系统设计

为了克服传统温湿度静态点测量的局限性大、灵活性差的问题,设计了一种基于无线传输的车载温湿度测量系统;用户通过计算机来无线遥控小车,可以进行人体无法进入或带有危险性质场所的温湿度测量;使用了DHT11数字式温湿度传感器进行温湿度的测量,并利用NRF905收发模块实现了数据的无线传输;上位机采用Labview图形化开发工具,控制面板上可以进行温湿度历史数据的查询,以曲线、数字、量程三种不同的形式显示实时温湿度数据,当温湿度超过预警值时能够报警,同时能实时显示小车运动轨迹;整个系统人机界面简洁,系统工作稳定,适应性强。     

一种尼龙老化评价的新方法

作为一种广泛使用的工程塑料,尼龙的老化备受关注。当作为电力系统芯片的封装材料时,尼龙在自然环境下的老化有可能会导致封装失效,从而影响芯片使用的可靠性,严重时甚至导致芯片的失效,给电力行业带来巨大损失。常规的自然老化和人工加速老化评价周期非常漫长,不同因素对尼龙老化的影响机理十分复杂,且这种影响难以研究,使得评价尼龙的老化稳定性成为一大难题。采用自主开发的原位老化评价系统,对尼龙6（PA6）和尼龙66（PA66）的老化稳定性及湿度对老化的影响进行了研究。该系统可以实现光照/温度/湿度/氧气等环境因素的加载,通过高灵敏度地测定材料在综合环境因素作用下产生的气相降解产物来评价材料的老化稳定性,评价时间缩短到几小时。实验表明,PA6和PA66的气相降解产物以H₂O和CO₂为主,由于H₂O在气相中的浓度不稳定,因此以CO₂的产生量作为老化评价指标。通过对不同自然老化时间PA6和PA66的原位老化评价,并与其ATR-FTIR红外光谱图进行对照,证明了原位老化评价方法能够较好地反映尼龙的老化程度,自然老化时间越长,PA6和PA66的稳定性越低,CO₂的产生量越大。进一步,采用该方法研究了湿度对PA6和PA66老化反应的影响,证明增大湿度对尼龙老化存在促进作用,而且升高温度会进一步促进湿度对老化的促进作用。研究表明,原位老化评价方法是一种快速评价尼龙老化稳定性及环境因素影响的有力手段。     

可见光/近红外光谱分析的木材树种与密度同时预测

光谱分析已经在木材特性参数（例如木材树种、气干密度、强度、含水率、表面粗糙度等）检测中得到应用,但是,现有的木材检测研究都只是针对上述某一项参数做数学建模和预测。如果需要检测木材多项参数,那么需要进行多次建模,并且每次建模预测时使用的数学模型类型（例如神经网络的类型）和内部结构参数一般各不相同。为了提高木材质量检测效率,提出了一种基于可见光/近红外光谱的木材树种和密度同时预测方法,它只需要一次建模和预测就可以实现这两项参数的同时输出。对东北5种常见木材（杨木、桦木、樟子松、白松和落叶松）进行检测,首先,采用K/S算法划分样本集,保证了训练集和预测集具有一定的代表性。然后,使用主成分分析和小波变换两种光谱降维方法,分别与BP神经网络和偏最小二乘支持向量机相结合建立了4种木材树种和密度同时预测模型和预测精度对比。 采用美国海洋公司的Ocean Optics USB2000-VIS-NIR微型光纤光谱仪采集样本的可见光/近红外光谱并进行预测处理,光谱范围为350～1 100 nm。结果表明,这四种模型都可实现对木材树种和密度的同时预测,其中小波变换降维方法结合偏最小二乘支持向量机所建立的模型预测效果相对较好,树种正确识别率为100%,训练集密度的R为0.973 4,预测集密度的R为0.940 8,训练集密度的RMSE为0.026 13,预测集密度的RMSE为0.038 46,它为同时对木材多项特性参数进行预测的便携式多功能一体化木材光谱检测仪器的开发奠定了理论基础。此外,还采用该公司生产的另一款光谱范围为900～1 650 nm的FLAME-NIR型微型光纤光谱仪进行了同样的实验。对比发现,利用FLAME-NIR型光谱仪所得出的结果整体比利用USB2000-VIS-NIR型光谱仪所得到的结果好,但是相差并不是很大。这说明该方法可用于对木材种类与密度的同时预测,而且具有一定的稳定性和精度,也节约了仪器的成本。     

Analysis of frost visualization over a fin and tube heat exchanger by natural convection

In this article, studies are made on frost formation and flow over a fin and tube heat exchanger due to natural convection for various conditions of relative humidity, air ambient temperature, and mean refrigerant temperature. The results include frost deposition, steps of frost formation, and its effect on heat transfer rate for different conditions. The results show that frost is formed only on the tip of the fins with higher thickness from top to bottom due to small distance between the fins. Frost causes to trap the air which increases the thermal resistance and reduces heat transfer in the system.     

2009年一次华北强桑拿天气过程的动力识别

本文数值模拟并诊断分析了2009年7月华北的一次桑拿天过程, 分析了高温高湿天气的环流特征, 温度、 湿度的水平和垂直分布特征, 位涡分布特征等. 分析发现, 此次桑拿天事件高层为反气旋性环流的高压控制, 水平分布图上, 低层相对湿度大. 垂直剖面上, 中低层为下沉气流和暖湿区, 有明显的水汽梯度和垂直温度梯度, 有倾斜的位涡分布. 既然桑拿天发生在夏季普遍高温的大环境之下, 因此靠单纯的温度或湿度来动力识别和诊断桑拿天, 有较大难度. 本文抓住华北地区桑拿天过程高温、 高湿、 高位涡的特点, 引入一个适合于桑拿天的湿热力位涡参数(MTPV, 它表示为▽ q · (▽ θ × ▽ Q), 这里q是湿度, 表示为大气或者云中水汽和所有水凝物的总和, θ 是位温, Q是位涡), 对桑拿天进行动力诊断分析, 并通过实际个例的计算分析作出简化. 个例分析发现, 此次高温高湿的桑拿天过程伴随MTPV的异常. 虽然2009年7月此次华北地区桑拿天过程有较高的温度, 较大的湿度和倾斜位涡发展, 但是单个变量的范围远大于我们要研究的华北地区桑拿天的爆发范围. 而结合这三个变量引入的MTPV及其简化形式, 无论从经向还是纬向剖面图来看, MTPV的异常大值区相对集中在北京及其周边的华北地区对流层的低层, 并维持. 因而, MTPV及其简化形式均能对此次高温高湿的桑拿天进行较好的动力识别。     

利用傅里叶变换红外光谱分析高温对木材-胶粘剂界面性能的影响

胶合木层板间界面起传递应力的作用,是构件承载的重要参数,其高温胶合性能决定了构件的抗火性能。以兴安落叶松结构材,以及结构用间苯二酚-酚醛树脂胶粘剂(PRF)和三聚氰胺-脲醛树脂胶粘剂(MUF)为研究对象,研究了20～280 ℃中木材含水率、密度、顺纹弦向抗剪强度和木材-胶粘剂界面胶合性能等216个试件在高温中的物理力学性能变化规律,通过傅里叶变换红外光谱分析高温中胶粘剂官能团变化,揭示了高温对木材-胶粘剂界面性能的劣化机理。结果表明,20～150 ℃时,兴安落叶松主要发生由水分释放导致的木材密度降低等物理反应,木材颜色未发生明显变化;150～200 ℃时,木材热降解开始,密度下降速度变缓,木材颜色逐渐加深;温度继续升高时,木材热降解加剧,颜色急剧加深,木材密度损失快速增加;当温度升至280 ℃时,木材发生炭化、完全转化为黑色,密度降至常温的72.49%。高温对兴安落叶松顺纹弦向抗剪强度有明显的劣化作用;20 ℃时木材抗剪强度为9.654 MPa,20～110 ℃时木材抗剪强度下降较快,150 ℃时降至常温的60.68%;150～280 ℃时,木材顺纹抗剪强度急剧下降,280 ℃时降至1.054 MPa。木材-胶粘剂界面的高温性能与胶粘剂的耐热性能密切相关;常温时,兴安落叶松与PRF和MUF均有较好的胶合性能,其界面抗剪强度分别为9.071和9.619 MPa,木破率均在80%以上;随着温度的升高,两种胶粘剂的界面抗剪强度均明显降低,木材-PRF界面较木材-MUF具有更好的耐高温性能。20～150 ℃时,两种胶粘剂界面抗剪强度劣化规律与木材抗剪强度相似,150 ℃时木材-PRF和木材-MUF的界面抗剪强度分别为常温的60.61%和60.92%,木破率均高于70%。150～280 ℃时,木材-PRF界面抗剪强度劣化规律仍与木材顺纹抗剪强度相似,280 ℃时降至0.774 MPa;木材-MUF界面胶合性能受温度影响更大,220 ℃时其木破率为10%,280 ℃时界面抗剪强度降至0 MPa。傅里叶变换红外光谱图中,20～150 ℃时PRF化学结构无明显变化;温度高于150 ℃时主要发生胶粘剂的进一步交联,以及醚键和亚甲基桥的断裂,PRF开始热解,但化学结构仍较完整;20～150 ℃时MUF的化学结构无明显变化,温度高于200 ℃时,羟甲基特征峰减弱、异氰酸酯基团产生,热降解剧烈,PRF较MUF具有更高的耐热性能。研究结果将为木结构工程合理选择原材料提供数据支撑,并为完善木结构抗火设计理论和方法提供依据。     

Analysis of the electrical characteristic of linseed oil films exposed to humidity

Linseed oil is a material widely used in various applications as a protecting layer for surfaces in industry, in scientific research, for medical use, and finally for artistic purpose. This natural origins substance has a particular application as a protective and smoothing layer on phenolic-melaminic laminate electrodes on Resistive Plate Chamber (RPC) detectors used in various particle physic experiments. In such electronic applications where linseed oil could be exposed to water vapours, an electrical characterization should result useful for having an overall control of the process involving the oil. In this paper, we studied the electrical behaviour towards relative humidity variations of linseed oil films deposited on interdigitated metal electrodes. Moreover, I/V characterisation both in air and vacuum, current vs. temperature and relative humidity was performed.     

δ2H, δ13C and δ18O from whole wood, α-cellulose and lignin methoxyl groups in Pinus sylvestris: a multi-parameter approach

Novel tree ring parameters – δ¹³C and δ²H from methoxyl groups – have been developed to reconstruct palaeoclimate. Tests with δ¹³C and δ¹⁸O derived from whole wood and cellulose samples, however, indicated differences in the isotopic composition and climate signal, depending on the extracted wood component. We assess this signal dependency by analysing (i) δ¹³C and δ¹⁸O from whole wood and cellulose and (ii) δ¹³C and δ²H from methoxyl groups, using Pinus sylvestris L. growing near Altenkirchen (Germany). Results indicate significant correlations among the time series derived from whole wood, cellulose, and lignin methoxyl groups. Compared with the whole wood samples, δ¹³C from methoxyl groups showed a different and overall lower response to climate parameters. On the other hand, δ²H from methoxyl groups showed high correlations with temperature and was also correlated with ring width, indicating its potential as a temperature proxy. Isotope time series with the highest correlation with climatic parameter were: (i) whole wood and cellulose δ¹³C with growing season precipitation and summer temperature; (ii) methoxyl groups with spring precipitation; (iii) whole wood and cellulose δ¹⁸O correlates with annual evapotranspiration and water balance; and (iv) methoxyl group δ²H with spring temperatures. These findings reveal that multiple climate elements can be reconstructed from different wood components and that whole wood proxies perform comparably to cellulose time series.     

汽车座椅局部散热除湿研究

车内空气的温度和相对湿度是影响人体舒适性的重要因素。特别是在高温条件下,高湿对人体的影响更加明显。使用计算流体力学和计算传热学的方法,对座椅和人体接触面温湿度较高的问题进行分析。根据人体及汽车座椅的相关尺寸,建立座椅的计算模型,然后进行数值计算。从改变结构的方面考虑解决问题的途径,即在座椅与人体接触面下开槽,并强制通风。使用FLUENT软件进行数值模拟,选择k-ε模型求解温度场和湿度场。计算结果表明,这种方法可以降低汽车座椅与人接触区域的温度和相对湿度,提高局部热舒适性。所得数据为车室内人体局部热舒适性评价提供理论依据。     

Proton transport through aqueous Nafion membrane

We introduce a new model for proton transport through a single proton-conducting channel of an aqueous Nafion membrane based on a mechanism in which protons move under electrostatic effect provided by the sulfonate ( SO₃ ^-groups of the Nafion side chains, the spin effect of active components, the hydrogen bonding effect with water molecules, and the screening effect of water media. This model can describe the proton transport within various levels of humidification ranging from the low humidity to the high humidity as a function of operating temperature. At low humidity, this model approaches to the so-called surface mechanism, while at high humidity, it approaches the well-known Grotthuss one. Proton motion is considered as the transfer from cluster to cluster under a potential energy. A proton-proton interaction is comprised in the calculation. Using Green function method, we obtained the proton current as a function of the Nafion membrane temperature. We found that the lower the temperature, the higher the proton current transfer through the Nafion membrane in low temperatures compared to the critical point 10K, which separates magnetic regime from non-magnetic regime. The increasing of proton current at very low temperatures is attributed to the spin effect. As the membrane temperature is higher than 40 ^° C , the decreasing of proton current is attributed to the loss of water uptake and the polymer contraction. The results of this study are qualitatively in good agreement with experiments. The expression for the critical temperature is also presented as a function of structural and tunable parameters, and interpreted by experimental data.     

木材/改性UF预聚体复合材料制备及性能表征

以人工林杨木为研究对象,利用改性脲醛预聚体浸渍并热压干燥处理,采用XRD,TGA,FTIR及SEM分析,对杨木改性处理前后物理化学变化进行了表征.结果表明:与杨木素材相比,改件材基本密度增加1.06倍,改性材抗弯强度提高33%,顺纹抗压强度提高74%,改性材的吸水性从104%降低到了 97%;改性剂的浸渍使得木材结晶度稍微降低,从39.65%降到了36.89%;TGA分析表明改性材的耐热性提高;FTIR分析表明改性材中的羟基有很好的缔合现象,并且羰基含量减少,醚键含最增加;最后SEM谱图分析了预聚体在改性材中的分布及存在状态.