不同形貌/晶型CdSe纳米材料的合成

以乙二胺(en)为溶剂, 通过调控反应物中镉源与硒源的摩尔比得到了不同形貌与晶型的CdSe纳米材料, 达到了同时调控形貌与晶型的目的. 当反应物中镉源与硒源摩尔比为1∶1时, 得到的产物为en体系常见的六方相棒状CdSe纳米晶体；当反应物中镉源与硒源摩尔比为1∶2时, 得到的产物为立方相CdSe纳米颗粒. 进一步研究结果表明, 反应体系中Se^2－离子生成的多少及速度是影响反应进程得到不同产物的关键.     

不同形貌/晶型CdSe纳米材料的简易合成

以乙二胺(en)为溶剂,通过调控反应物中镉源与硒源的摩尔比得到了不同形貌与晶型的CdSe纳米材料,达到了同时调控形貌与晶型的目的.当反应物中镉源与硒源摩尔比为1:1时,得到的产物为en体系常见的六方相棒状CdSe纳米晶体;当反应物中镉源与硒源摩尔比为1:2时,得到的产物为立方相CdSe纳米颗粒.进一步研究结果表明,反应体系中Se2-离子生成的多少及速度是影响反应进程得到不同产物的关键.     

Cu_7S_4纳米管的生物分子辅助水热合成与光学性质(英文)

使用生物分子DL-甲硫氨酸辅助水热方法合成Cu7S4纳米管,产物的形貌与晶型可通过改变实验参数进行调控.研究表明,硝酸铜和DL-甲硫氨酸在反应开始时的配位比为1∶2,而且当反应物的摩尔比为1∶2和反应温度为200℃时可合成直径为100-600nm、长度达40-100μm的多晶Cu7S4纳米管.使用D-或L-甲硫氨酸均能得到类似Cu7S4纳米管.Cu7S4纳米管的禁带宽度为2.88eV,与Cu7S4的块体材料相比有明显蓝移.基于实验研究结果,讨论了甲硫氨酸分子中的官能团与反应产物之间的联系并提出了Cu7S4纳米管的自牺牲模板法形成机理.     

反应条件对乳液法自组装合成氧化锰纳米粒子结构、形貌和尺寸的影响

通过改变反应物物质的量比、分散相与连续相体积比、反应体系温度和煅烧后处理温度,研究了反应条件对乳液法自组装合成氧化锰纳米粒子结构、形貌和尺寸的影响.结果表明:当高锰酸钾与油酸物质的量比在1∶5～1∶1之间时,形成蜂窝状纳米粒子和空心纳米粒子;当分散相(油酸)与连续相(水)的体积比为4∶200时,形成良好的空心球纳米结构;反应体系温度升高不利于产物的洗涤;不同温度的煅烧后处理不仅影响氧化锰纳米粒子的形貌,而且影响其结晶度和晶型.     

微/纳米ZnO粉体在Glu-BF_4离子液体水溶液中的诱导生长

以一定浓度谷氨酸-氟硼酸(Glu-BF_4)离子液体水溶液为反应介质,摩尔比为1∶6的二水合醋酸锌和氢氧化钠为反应物,在室温下制备前驱体,再通过微波辅助加热制备了具有绒球形貌的微/纳米ZnO粉体.利用扫描电子显微镜(SEM)、X射线衍射仪、比表面积测试仪、能谱仪、拉曼光谱仪和透射电子显微镜(TEM)等对产物形貌、晶型、比表面积、组成和晶面分布进行了测定.结果显示,所得产物为六方晶系纤锌矿结构,平均粒径20.4 nm,绒球大小1.6~3.0μm,比表面积为28.3 m~2/g,产物纯度较高.当反应物浓度一定,离子液体浓度分别为0.02,0.04,0.08和0.12 mol/L时都得到了类似形貌的微/纳米ZnO粉体,且随着离子液体使用量的增加,绒球尺寸分布更加均一.当离子液体浓度一定,而反应物浓度逐渐下降时,产物形貌发生递变性变化.ZnO晶粒在Glu-BF_4离子液体诱导下首先生成不规则的纳米片,纳米片进一步聚集,在一定反应物浓度范围内生成绒球形貌粉体,反应物浓度较低时只生成绒球的核心部分,而浓度更高时则生成纳米针阵列.通过不同条件下纳米ZnO粉体形貌变化规律,探讨了强碱性条件下Glu-BF_4离子液体水溶液中微/纳米ZnO粉体的生长机制.     

6-巯基烟酸修饰的CdSe纳米晶的合成及应用

以6-巯基烟酸(6-MNA)为修饰剂,在水溶液中合成CdSe纳米晶,考察了pH值、反应物不同配比、反应温度及反应时间等条件对合成CdSe纳米晶荧光强度的影响,获得最佳合成条件为:反应物配比Cd2+∶HSe-∶6-MNA=1∶0.5∶3,溶液pH值为9.70,回流温度60℃,回流时间30min。透射电镜观察所合成的纳米晶形貌为树状,与传统的球状不同,激发及发射波长分别位于400nm和543nm,与传统的球状纳米晶相似。同时考察了缓冲溶液的体积与pH值、反应温度、反应时间对体系荧光强度的影响。在最佳实验条件下,体系的荧光强度与牛血清白蛋白(BSA)的浓度呈线性关系,线性范围为0～4.5×10-7mol/L,相关系数R=0.9851,检出限为1.0×10-8mol/L。该方法用于合成样及实际样品的测定,结果令人满意。     

CdSe微米球的水热合成及表征

用合成的硒代硫酸钠作为硒源,Cd(NO3)2·4H2O作为Cd源,通过控制配位剂与反应物的比例及表面活性剂的加入,在水溶液中合成了球状的CdSe微米晶.产物用X射线衍射仪,扫描电子显微镜、透射电子显微镜进行表征.结果表明:此法合成了结晶性良好的六方相的CdSe微米晶.并探讨了可能的生长机理.     

介观结构SiO2/CdO纳米复合物为前驱体原位水热合成半导体CdSe和CdS纳米晶

以高度有序的介观结构SiO₂/CdO纳米复合物为前驱体,在硒源或硫源存在的还原性条件下,利用原位水热反应,合成了介观结构SiO₂/CdSe及SiO₂/CdS纳米复合物,除去SiO₂后,得到半导体CdSe及CdS纳米晶.通过X射线衍射(XRD),高分辨率透射电镜(HRTEM),X射线能散射谱(EDX)及选区电子衍射(SAED)等手段对产物进行了组成和结构表征.结果表明,介观结构SiO₂主体材料在合成过程中起到了一定的形貌和尺寸限制作用,得到的CdSe和CdS均为直径在8 nm左右的类球形六方相纳米晶.     

十六烷基胺稳定的CdSe纳米晶体的合成与表征

用CdO通过高温化学方法制备了具有高发光特性的CdSe胶体纳米晶.通过改变配体十六烷基胺在反应体系中的含量,合成了3种不同粒径的CdSe纳米晶.利用TEM、XRD和光谱等手段对合成出来的CdSe纳米晶的形貌结构和发光特性进行了表征.结果表明,随着十六烷基胺在反应体系中量的增多,CdSe纳米晶的粒径增大.通过调整十六烷基胺在反应体系中的量可以方便地控制纳米晶的尺寸.     

LiFePO4纳米晶的尺寸、形貌调控及锂电池性能研究

由于材料的电化学性能与其尺寸、形貌和结构密切相关,本文围绕乙二醇体系制备LiFePO_4纳米晶展开了材料的尺寸和形貌调控合成探索,并对材料进行了锂电池性能表征。改变体系的反应物浓度,LiFePO_4纳米晶的尺寸明显发生变化,当体系中FeSO_4的浓度为0.15mol/L时,得到的LiFePO_4纳米晶尺寸最小,其锂离子电池的容量稍高于其他尺寸的LiFePO_4纳米晶。葡萄糖的添加量对LiFePO_4纳米晶的形貌会产生影响,但对锂离子电池性能影响不大。     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。     

LOW DENSITY POLYETHYLENE/CLAY NANOCOMPOSITES MODIFIED BY ETHYLENE COPOLYMERS： EFFECTS OF FUNCTIONALIZED SEGMENTS ON MORPHOLOGY

Melt extrusion was used to prepare binary nanocomposites of ethylene copolymers and organoclay and trinary nanocomposites of low-density polyethylene （LDPE）, ethylene copolymer and organoclay. X-ray diffraction （XRD） and transmission electron microscopy （TEM） were used to analyze the structure of the clay phase and the morphology of the nanocomposites. Influences of the comonomer in the copolymer and the content of the copolymer on the morphology of the resulting nanocomposites were discussed. The binary and the trinary composites may form intercalated or exfoliated structures depending on the interaction between the copolymer and the clay layers and the content of the copolymer.     

电流变液中悬浮颗粒的体积与形状的变化

基于偶极近似,运用电极化方法,定量研究了电流变液中悬浮颗粒在外电场作用下其体积和形状的变化,并计算了其体积和形状的相对变化率.研究结果表明:悬浮颗粒的体积和形状的相对变化率均与电场强度的平方成正比,并与ER本身的性质有关.一般情况下,颗粒的体积和形状的相对变化率分别为8.4%和12.5%,对总体积变化率的贡献为1.68%.这种变化对于ER系统的电涨和电热都作出了贡献,仅当将颗粒当作刚性球时,其自由能才与电场强度的平方成正比.     

Phenolic potential of Tannat, Cabernet-Sauvignon and Merlot grapes and their correspondence with wine composition

The phenolic potential of Tannat, Cabernet-Sauvignon and Merlot grapes was evaluated in 2001 and 2002 and its correspondence with the colour and composition of the respective wines was established. Three vineyards of each variety, situated in the south of Uruguay were considered. Two samples of each vineyard were taken at the moment of the harvest. Phenolic richness, extractable anthocyanins contents and total potential in anthocyanins of the grapes were estimated. Two fermentations on skins were carried out for each vineyard using 50 kg of grape in each one. The anthocyanic and total polyphenols contents of the musts were analysed every 24 h, and skins extractions were carried out in parallel in the laboratory. The duration of the maceration for each variety was decided in function of the analytical results in the grapes, musts and skins extractions. Wines were analysed 2 months after the alcoholic fermentation, determining its phenolic composition and colour. Tannat grapes presented anthocyanic and total polyphenols contents significantly higher in both years. Therefore, wines from this variety presented colour intensity and phenolic contents statistically higher than Cabernet-Sauvignon and Merlot. The correlations between the phenolic contents of the grapes, skins, musts and wines were very significant. Colour intensity and phenolic contents of the wines were highly correlated with the total polyphenols of the grapes and with anthocyanins of the grapes, skins, musts and wines. The estimate of the phenolic potential of the grapes and the extractability of the pigments allows to manage more adequately the fermentation on skins and is an interesting tool to predict the colour and the composition of the wines.     

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANOMONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.     

Applications of Thermal Analysis and Coupled Techniques in Pharmaceutical Industry

Thermal analysis methods are well-established techniques in research laboratories of pharmaceutical industry. The robustness and sensitivity of instrumentation, the introduction of automation and of reliable software according to the industrial needs widened considerably the areas of applications in the last decade. Calibration of instruments and validation of results follow the state of the art of cGMP as for other analytical techniques. Thermal analysis techniques are especially useful for the study of the behavior of the poly-phasic systems drug substances and excipients and find a unique place for new delivery systems. Since change of temperature and moisture occur by processing and storage, changes of the solid state may have a considerable effect on activity, toxicity and stability of compounds. Current requirements of the International Conference of Harmonisation for the characterization and the quantitation of polymorphism in new entities re-enforce the position of thermal analysis techniques. This challenging task needs the use of complementary methods. Combined techniques and microcalorimetry demonstrate their advantages. This article reviews the current use of thermal analysis and combined techniques in research and development and in production. The advantage of commercially coupled techniques to thermogravimetry is emphasized with some examples. This revised version was published online in August 2006 with corrections to the Cover Date.     

3,7-二硝基亚氨基-2,4-二氮杂双环[3,3,0]辛烷的放热分解反应动力学

The kinetic parameters of the exothermic decomposition reaction of the title compound in a temperature-programmed mode have been studied by means of DSC. The DSC data obtained are fitted to the integral, differential and exothermic rate equations by linear least-squares, iterative, combined dichotomous and least-squares methods, respectively. After establishing the most probable general expression of differential and integral mechanism functions by the logical choice method, the corresponding values of the apparent activation energy (Ea), pre-exponential factor (A) and reaction order (n) will be obtained by the exothermic rate equation. The results show that the empirical kinetic model function in differential form and the values of Ea and A of this reaction are (1-α)0.44, 230.4 kJ/mol and 1018.16 s-1, respectively. With the help of the heating rate and obtained kinelic parameters, the kinetic equation of the exothermic decomposition reaction process of the title compound is proposed. The critical temperature of thermal explosion of the compound is 302.6℃. The above-mentioned kinetic parameters are quite useful for analyzing and evaluating the stability and thermal change rule of the title compound.     

多弧离子镀TiN与不同金属基材间的接触界面与表面特性

用多弧离子镀技术在不同金属基材上进行TiN镀膜实验,制备了TiN/Fe、 TiN/Cu和TiN/Cr/Cu复合膜.借助扫描电子显微镜(SEM)、 X射线衍射仪(XRD)和光电子能谱(XPS),研究了TiN与Fe、 Cu和Cr/Cu三种不同衬底接触界面的形貌、结构及其表面特性.SEM观察发现,在一定离子镀膜条件下, TiN涂层可与Fe、 Cu和Cr/Cu金属基材形成均匀平整的接触界面,在铜基上TiN界面清晰,在Fe与Cr/Cu界面有明显的层状晶界微结晶分布.XRD分析显示, Fe、 Cu和Cr/Cu表面生成的薄膜都包含TiN、 Ti2N等多晶相,在Cr/Cu界面还包含Ti-Cr的金属间化合物.XPS结果表明,表面除了TiN膜外,还生成TiO2和TiOxNy等氧化膜.Ar+刻蚀5 min后, TiO2消失, TiOxNy减少, TiN则呈增加趋势.TiN与Cr/Cu界面形成明显的Ti-Cr和Cr-Ni互扩散层,这有助于增强薄膜附着力,形成较牢固的TiN涂层.     

作为一种城市研究范式的“都市马克思主义”

非马克思主义者由于不能以实践的观点和辩证的观点理解城市而无法发展出一种总体性的城市理论。马克思和恩格斯虽然提供了以历史唯物主义分析城市问题和都市形式的线索,但也引发了“城市中的社会”研究还是“城市社会”研究的争论。随着人类城市化进程的不断深化,理论和实践两方面的诉求使澄清作为一种城市研究范式的“都市马克思主义”成为当前之需。马克思主义探究的社会现实是人类生产自己生活方式的具体的总体,而城市是人类生产自己生活的一定方式,因此研究城市必须将其放置于人类生产活动构成的社会总体之中。当今时代,都市已成为人类生产自己生活的自觉方式和社会历史发展的主导性构成。作为城市研究的马克思主义范式和马克思主义的当代哲学范式,都市马克思主义以包含着丰富矛盾性的“都市”为理论总问题,以实践的观点辩证地理解和揭示现代世界的都市现实,是一种微观视域和宏观视域相结合,真正探究现实的人的生存状况、生存矛盾、生活方式和生活意义的社会历史理论。具体来说,它致力于建构都市的社会历史解释模式,展开都市政治经济学批判和都市文化批判,提供与人类解放实践相连的都市革命理论。