液体离子提取烟梗木质素的研究（英文）

本文研究了在温和的条件下利用四种离子液体对烟梗木质素的提取过程,结果表明1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])的提取效果最佳.通过80℃的热水搅拌30 min的预处理过程可以有效脱除烟梗中含有的绝大多数糖分同时疏松了烟梗的微纤维结构,在此基础上使用[EMIM][DEP]在150℃和反应时间4 h的条件下可以获得纯度90.21%的木质素,木质素的提取率达到85.38%.     

[EMIM][A_C]在高压下的比定压热容

离子液体1-乙基-3-甲基咪唑醋酸盐([EMIM][A_C])广泛应用于化学分离过程,但其在高压下的比定压热容数据比较缺乏。本文基于流动型量热法建立了一套可适用于高压流体比定压热容测量的实验系统,温度、压力、比定压热容的扩展不确定度分别为0.05 K,13 kPa和0.98%。利用该实验系统对[EMIM][A_C]在T=(303~393)K、p=(0.1~16)MPa范围内的比定压热容进行了测量。基于测量结果,建立了一个可以精确计算[EMIM][A_C]比定压热容的新公式。     

离子液体中聚氧化乙烯(PEO)相变过程中的氢键效应

我们把Flory-Huggins模型推广应用到聚合物/离子液体体系,研究聚氧化乙烯(PEO)在离子液体[EMIM][BF_4]中相变过程中的氢键效应,理论模型考虑了三种类型氢键(Ⅰ型:PEO-[EMIM]~+氢键,Ⅱ型:PEO-[BF_4]~-氢键和Ⅲ型:[EMIM]~+-[BF_4]~-氢键)的形成,分析了三种类型的氢键分数随温度、 PEO体积分数的变化.研究发现,三种类型的氢键分数随温度的升高而减少.在较小PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数轻微地减小;在较大PEO体积分数条件下,增加PEO体积分数,Ⅰ型、Ⅱ型氢键分数急剧减少.Ⅲ型氢键分数随着PEO体积分数的增加而急剧降低.由于三种氢键效应,第二维里系数A_2随温度的增加而减小.通过计算分析不同分子量的PEO在[EMIM][BF_4]中的相图发现,在PEO体积分数较低的条件下,Ⅰ型、Ⅱ型和Ⅲ型氢键是PEO相变的主要驱动力;在PEO体积分数较高的条件下,Ⅰ型和Ⅱ型氢键在PEO相变过程中起到主导作用.     

母乳常温及低温保存期的研究

为研究母乳的保质问题,实验测定了母乳在常温(20℃),冷藏(4℃)和低温(-18℃)存放时的保存期。并以母乳存放在低温(-18℃)为例,测量了其新鲜度及其蛋白质,脂肪等营养成分的变化规律.研究显示,新鲜母乳在20℃下,能存放5-6小时左右。在4℃条件下,存放时间能达到3—5天左右。在-18℃下,母乳的营养成分在前三个月变化不大.四个月后蛋白质、脂肪含量分别下降了30%,60%左右;酸度由17.94°T上升至21.44°T。在此条件下,可以保存四个月。     

液体工质对气液热声发动机性能影响的实验研究

采用气液耦合振动是降低热声发动机谐振频率和提升其压力振幅的一种有效途径。为了研究液体工质对于气液热声发动机性能的影响,本文针对水、室温离子液体[EMIM][BF₄]、20%氯化钾溶液、40%和50%甲酸钾溶液五种液体工质进行了实验研究和分析。实验数据显示,在相同加热功率下,采用50%甲酸钾溶液时系统谐振频率最低,而水工质对应的谐振频率最高;40%甲酸钾溶液的压力振幅最大,而采用离子液体[EMIM][BF4]时系统压力振幅最小。研究结果表明:采用密度较大的液体工质可获得较低的谐振频率,而密度大、黏度小的液体工质则有利于获得更大的压力振幅。     

埋层界面和空气表面和频光谱信号贡献的调控

本文研究表明通过膜厚控制和表面等离激元增强方法可有效区分隐藏界面和空气表面的和频振动光谱信号. 以氟化钙基底支撑的PMMA薄膜为模型,观察到隐藏界面和空气表面对和频信号贡献的变化. 通过监控羰基和甲基伸缩振动基团,发现薄PMMA膜的和频信号来自PMMA/空气表面的化学基团-CH₂、-CH₃、-OCH₃和C=O,而厚PMMA膜的和频信号则来自基底/PMMA埋层界面的-OCH₃和C=O基团. 随制膜浓度增大,埋层界面C=O基团的取向角从65°下降到43°,且浓度大于或等于0.5 wt%时,取向角等于45°±2°. 相比之下,空气表面C=O的取向角落在21°∽38°之间. 在金纳米棒存在条件下,表面等离激元可以极大地增强和频信号,尤其是来自埋层界面信号.     

Pb(Sc_(1/2)Nb_(1/2))O_3中有序-无序转变和铁电相变的Raman光谱研究

采用wolframite前驱物法制备了Pb(Sc1/2Nb1/2)O3陶瓷。通过调节陶瓷烧结工艺,获得了三种具有不同B位离子有序度的PSN陶瓷。测量了三种陶瓷样品在室温至160°C范围内的Raman光谱随温度变化。结果表明,随着温度的升高,三种不同B位有序度的陶瓷样品中,Raman光谱中位于530 cm-1的F2g模的峰位和半峰宽分别在100°C,85°C和80°C发生了突变,表明陶瓷分别在100°C,85°C和80°C三个温度点发生了铁电-顺电相变。上述结论得到了介电温度谱测量数据的支持。     

光致电化学法提高垂直结构发光二极管出光效率的研究

研究了在垂直结构发光二极管(VLED)器件中, 光致电化学法(PEC)刻蚀N极性n-GaN的速率受不同刻蚀条件(刻蚀浓度、刻蚀时间和光照强度)的影响. 并选择N极性n-GaN表面含有较理想六角金字塔结构(侧壁角为31°)的样品制成器件, 研究PEC刻蚀对VLED的欧姆接触和光电性能的影响. 结果表明, 与未粗化样品相比, PEC刻蚀后的样品接触电阻率明显降低, 形成更好的欧姆接触; 其电学特性有较好的改善, 光输出功率有明显提高, 在20 mA电流下光输出功率增强了86.1%. 对不同金字塔侧壁角度的光提取效率用时域有限差分法(FDTD)模拟, 结果显示光提取效率在侧壁角度为20°– 40°有显著提高, 在23.6° (GaN-空气界面的全反射角)时达到最大.     

基于数值模拟的飞行员高速气流吹袭损伤分析

研究飞行员高速气流吹袭的损伤机理,应用尺度适应模型对人椅系统外流场进行数值模拟.在马赫数为0.6,迎角为-90°~90°条件下的数值计算结果与风洞试验结果吻合较好.对不同马赫数、不同迎角的无防护状态下的人椅系统进行数值模拟,研究发现高速气流吹袭下飞行员面颈部、胸腹部、上臂内侧、小腿迎风侧压力较大;增大人椅系统的迎角可以改善飞行员身体各部分的受力情况.     

共沉淀ZnO/γ-Al2O3体系EXAFS研究

用XRD和EXAFS研究了200°C,300°C,450°C,800°C焙烧的共沉淀ZnO/γ-Al₂O₃体系.通过EXAFS分析得到了Zn原子的径向分布函数,并针对第一配位层做了定量的拟合,结果是体系中第一层锌氧Zn-O保持ZnO中的四配位结构.文中还对第二层配位峰的变化趁势做了分析.     

Effect of cellulose–lignin interactions on char structural changes during fast pyrolysis at 100–350 °C

This study investigates the cellulose–lignin interactions during fast pyrolysis at 100–350 °C for better understanding fundamental pyrolysis mechanism of lignocellulosic biomass. The results show that co-pyrolysis of cellulose and lignin (with a mass ratio of 1:1) at temperatures < 300 °C leads to a char yield lower than the calculated char yield based on the addition of individual cellulose and lignin pyrolysis. The difference between the experimental and calculated char yields increases with temperature, from ～2% 150 °C to ～6% at 250 °C. Such differences in char yields provide direct evidences on the existence of cellulose–lignin interactions during co-pyrolysis of cellulose and lignin. At temperatures below 300 °C, the reductions in both lignin functional groups and sugar structures within the char indicate that co-pyrolysis of cellulose and lignin enhances the release of volatiles from both cellulose and lignin. Such an observation could be attributed to two possible reasons: (1) the stabilization of lignin-derived reactive species by cellulose-derived reaction intermediates as hydrogen donors, and (2) the thermal ejection of cellulose-derived species due to micro-explosion of liquid intermediates from lignin. In contrast, at temperatures ≥ 300 °C, co-pyrolysis of cellulose and lignin increases char yields, i.e., with the difference between the experimental and calculated char yields increasing from ～1% at 300 °C to ～8% at 350 °C. The results indicate that the cellulose-derived volatiles are difficult to diffuse through the lignin-derived liquid intermediates into the vapor phase, leading to increased char formation from co-pyrolysis of cellulose and lignin as temperature increases. Such an observation is further supported by the increased retention of cellulose functional groups in the char from co-pyrolysis of cellulose and lignin.     

Primary release and transformation of inorganic and organic sodium during fast pyrolysis of sodium-loaded lignin

This study employs a wire-mesh reactor (WMR) to understand the primary release and transformation of inorganic and organic sodium during fast pyrolysis of various sodium-loaded lignin samples at 300–800 °C. Due to the minimization of volatile-char interactions in WMR, the overall sodium release during lignin pyrolysis is relatively low, i.e., ∼9–11% and ∼7–14% for the inorganic and inorganic sodium loaded lignin, respectively. The presence of the inorganic sodium in the condensed volatiles (so-called oil) clearly indicates the important role of thermal ejection in the release of the inorganic sodium, since sodium salts are unlikely to evaporate under current conditions. While the release of the organic sodium into oil can be due to both thermal ejection of aerosols and evaporation of low carboxylates. Despite the low sodium release, significant transformation of the inorganic and organic sodium can take place during lignin pyrolysis. For the inorganic sodium loaded lignin, the inorganic sodium decreases continuously from ∼67% at 300 °C to ∼42% at 800 °C, accompanied by a steady increase in the organic sodium (i.e., the ion-exchangeable sodium) from ∼17% at 300 °C to ∼37% at 800 °C. While for the organic sodium loaded lignin, its transformation into the inorganic sodium is faster at higher temperatures, leading to a large increase in the inorganic sodium (i.e., carbonates) from ∼9% at 300 °C to ∼48% at 800 °C, as well as a reduction in the organic sodium from ∼79% at 300 °C to ∼28% at 800 °C. The data generated in this study will be important to understand the catalytic mechanism of sodium during thermochemical processing of alkali lignin for the production of bioenergy and biofuels.     

Synthesis of Lignin-Based Thermoplastic Copolyester Using Kraft Lignin as a Macromonomer

Lignin-based thermoplastic copolyester was synthesized for eco-friendly polymers and composite applications using lignin as a macromonomer to form a high molecular weight polymer. Kraft lignin was polymerized with sebacoyl chloride in the presence of triethylamine in N,N-dimethylacetamide (DMAc), and the molecular weight of the synthesized polymer was controlled by the polymerization temperatures and [COCl]/[OH] ratios providing up to 39 000 corresponding to 4–5 repeating units of lignin macromonomers. The glass transition temperature of the synthesized polymer was difficult to measure due to the random distribution of functional groups and irregular configurational or conformational arrangement of natural lignin. Therefore, the complex electric modulus (CEM) technique was used to determine the glass transition of the synthesized polymer to give around 70°C measured by the peak of the imaginary part of CEM. The synthesized lignin-copolyester exhibited good thermal stability up to 200°C in TGA analysis and, thus, it was possible to shape the synthesized polymer using the solvent casting or hot-melt processing techniques at 120°C–140°C without generating odor, fume or irritation. Although the molecular weight should further be increased in the future, the developed methodology may help to exploit new applications for eco-friendly sustainable materials in various fields.     

Purification of waste water of cellulose production from rape straw by oxidation in supercritical aqueous media

Purification method of waste water by oxidation in supercritical aqueous media (OSAM) has been considered. It is shown that the achievement of acceptable parameters of waste water for biological treatment plants is possible upon combining of a coagulative-flocculative process with OSAM. The need for such a combination is determined by the insufficient degree of degradation of lignin using only OSAM, conducted at 400°C and 24 MPa (oxidizer–H₂O₂).     

Generalized two-dimensional correlation infrared spectroscopy to reveal the mechanisms of lignocellulosic biomass pyrolysis

As the initial stage of combustion, pyrolysis plays a significant role in the combustion of biomass, a typical solid fuel that contains higher volatile contents than other solid fuels. To better understand the pyrolysis mechanism, we herein employed generalized two-dimensional correlation infrared spectroscopy (2D-PCIS) to analyze the functional group evolution in bamboo chars between 250 and 600 °C, and by combination of the volatile release properties, the biomass pyrolysis process mechanism was speculated. We found that below 250 °C, the hydrogen bonding network within the biomass macromolecular structure was broken, while at 250–300 °C, the branched structures were broken during hydration and decarboxylation reactions, resulting in the formation of H₂O, acetic acids, and CO₂. The subsequent formation of various phenols between 300 and 350 °C mainly originated from rupture of the ether bridges in the lignin structure. In addition, molecular rearrangement of the intermediates from the decomposition of holocellulose resulted in aromatic ring formation. Interestingly, analysis by 2D-PCIS demonstrated that the aromatic rings bearing adjacent substituents easily formed double active sites following breakage of the branched structures. These structures then easily produced fused ring systems below 400 °C, while dehydrogenation and polycondensation at?>?400 °C promoted the formation of fused rings from aromatic rings without adjacent substituents.     

Dielectric properties of Bi<Subscript>2</Subscript>PbNb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics prepared by different techniques

Different techniques for the synthesis of Bi₂PbNb₂O₉, namely the mixed oxide technique, molten salt synthesis, hydrothermal synthesis, co-precipitation and the tartaric acid gel method were investigated and the results on the dielectric properties are reported. The heat-treatment of the precursor powders was the same for all precursor powders. Sintering at 1040 °C under ambient pressure resulted in polycrystalline specimens, while hot-forging at 1040 °C with a pressure of 20 MPa produced c-axis aligned samples. Phase composition and crystallite orientation of the sintered bodies were analyzed by X-ray diffraction. Single-phase material was obtained in all cases. Hot-forging not only yielded c-axis orientation, but also increased the relative densities above 99.4%. The relative permittivity decreased for c-axis oriented material compared to polycrystalline ceramics. Values for the relative permittivity for the hot-forged specimens at 100 °C at 100 kHz varied between 165 and 250, depending on the fabrication method. The Curie temperature for the c-axis aligned samples was 568 °C, independent of the nature of the precursor powders. PACS 77.22.-d; 77.84.-s     

The reusability characteristics of LiF:Mg,Cu,P with a maximum intensity at 280 °C in an environment with elevated temperature

Efforts are aimed at finding a method that could serve TL dosimetric measurements in the range of low-dose but carried out in an environment with elevated temperature. The temperature at the position of the maximum intensity of LiF:Mg,Cu,P was about 280 °C when annealed at 460 °C. LiF:Mg,Cu,P with a maximum intensity at 280 °C should present good thermal stability. The TL intensity of LiF:Mg,Cu,P with a maximum intensity at 280 °C was about 54% of the standard LiF:Mg,Cu,P, it should have a minimum measurable dose in the range of micro-Gy. LiF:Mg,Cu,P with a maximum intensity at 280 °C could be re-used by the 660 °C/30 min annealing, followed by 270 °C/20 min, 240 °C/10 min and 460 °C/30 min. It's possible for LiF:Mg,Cu,P to be extended application for low dose test in an environment with elevated temperature.     

Pyrolysis study of poplar biomass by tunable synchrotron vacuum ultraviolet photoionization mass spectrometry

Pyrolysis is one of the most important methods to convert biomass into biofuel, which is a potential substitute for fossil fuel. The pyrolysis process of poplar biomass, a potential biofuel feedstock, has been studied with tunable synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry (PIMS). The mass spectra at different photon energies, temperatures, and time-evolved profiles of selected species during poplar pyrolysis process were measured. Our results reveal that poplar is typical of hardwood according to its relative contents of three lignin monomeric precursors. As temperature increases from 300 to 700 °C, the overall intensities of pyrolysis products decrease due to the gas-phase cracking. Observed intensities of syringyl and guaiacyl subunits of lignin in poplar at low temperature present different trends: the intensities of syringyl subunits of lignin undergo an increase firstly and then a decrease, whereas those of guaiacyl subunits of lignin show decrease continuously. Time-dependent data demonstrate that hemicellulose pyrolysis is faster than lignin in poplar. This work reports a new application of SVUV PIMS in biomass pyrolysis, which performs very well in products analysis.     

Optical behaviour of melting for a thin metal film

Reflectance measurements have been performed for gallium films at normal incidence (from 0.3 to 0.9 μm) in terms of temperature (from -20°C to + 40°C). The basic results are: (i) a drastic change in reflectance when melting occurs (about 20% at 0.6 μm), and (ii) a shift in the temperature of the solid-liquid transition with the thickness of the film which only takes place on and after the second melting (about 7°C for a film 250A?thick).     

Study on Properties and Structure of Near Melt Point Extruded High‐Density Polyethylene

The effect of extrusion temperature on the mechanical properties of high‐density polyethylene (HDPE) was examined using solid‐state extrusion (SSE) and melt‐state extrusion (MSE) techniques. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) investigations were employed to provide evidence for explaining the relationship between mechanical properties and morphology of extrusion moldings. Extruded from a convergence‐divergence die, compared with samples obtained by MSE, the yield strength of samples obtained by SSE was enhanced in both longitudinal and transverse directions with a ductile failure. The yield strength decreased sharply with increasing extrusion temperature. The maximum longitudinal yield strength of samples extruded at 112°C was 181 MPa with an 87% elongation at break; the corresponding values were 28 MPa and 800% for samples extruded at 140°C (MSE); in the transverse direction the yield strength was 27 MPa with a 101% elongation at break for samples extruded at 140°C, while the maximum yield strength was 51 MPa with a 45% of elongation at break for samples extruded at 116°C. Compared with sheets extruded at 140°C, DSC data shows a 5.3°C increase in melting point, a 9.5°C decrease in melt point width, and a 7.1% decrease in crystallinity for sheets extruded at 112°C. SEM indicates that spherulites predominate in MSE samples, while a preferred orientation of the lamellae along the extrusion direction were mainly produced by SSE.