纳米Y_2O_3∶Eu~(3+)超声辐射沉淀制备及其性能研究

采用超声辐射沉淀法以草酸为沉淀剂制备出纳米Y2 O3 ∶Eu3 + 粉体。利用XRD、TG DTA、TEM等手段对其进行了表征 ,并对其光谱特性进行了研究。结果表明 :将超声辐射引入普通沉淀法中 ,可显著提高粉体性能 ,所得纳米Y2 O3 ∶Eu3 + 为球形 ,粒度分布均匀 ,粒径约为 38～ 4 5nm ,与微米晶相比 ,该纳米晶的发射光谱发生蓝移 ,激发光谱发生红移。     

Y2O3:Eu纳米晶的硝基取代苯甲酸配合物固相热解制备和性能

以苯甲酸、邻硝基苯甲酸、间硝基苯甲酸、对硝基苯甲酸、3，5－二硝基苯甲酸等为配体制备了Y^3 、Eu^3 二元配合物，配合物中Y^3 与Eu^3 的摩尔比为9：1，利用这些配合物的爆炸式热分解特性通过固相热解反应制备了一系列Y2O3：Eu纳米晶。透射电镜观察，可以看出所得纳米晶呈球形，粒度介于40－60nm，X射线衍射分析表明实验所得纳米晶属立方晶系，粒径与电镜观察所得结果基本一致；Eu^3 的引入并不影响Y2O3的晶相组成；配体类型对纳米晶的结构没有显著影响，不过相对于硝基取代苯甲酸配合物，苯甲酸配合物热解所得Y2O3：Eu纳米晶团聚严重；退火温度显著影响纳米晶粒度，退火温度高，纳米晶粒度大，反之亦然。荧光光谱测定表明所有Y2O3：Eu纳米晶具有相似的发光行为，其中以苯甲酸配合物分解所得Y2O3：Eu纳米晶发光性能最为优越。     

Y2O3：Eu^3＋发光薄膜的溶胶—凝胶法制备、表征及图案化

采用Pechini溶胶－凝胶法制备了纳米级Y2O3：Eu^3 发光薄膜，同时，通过软石印技术得到了条纹宽度为5－60μm的Y2O3：Eu^3 图案化发光薄膜，通过X射线衍射（XRD），付里叶变换－红外光谱（FT－IR），原子力显微镜（AFM），光致发光（PL）光谱及寿命等方法对得到的发光薄膜进行了表征，XRD结果表明500℃时薄膜开始结晶，900摄氏度已结晶完全，得到了立方相的产物，图案化的条纹在烧结的过程中发生了明显的收缩（50％），Y2O3基质向掺杂的稀土离子Eu^3 发生了有效的能量传递，使得Eu^3 显示出5D0－7FJ（J＝0，1，2，3，4）特征发射，寿命和光致发光光谱的研究表明，发光强度随着温度的升高而增强。     

立方晶型Sb2O3纳米晶的合成及光催化性能

采用沉淀法合成了立方晶型Sb2O3纳米晶,通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)和电子自旋共振谱(ESR)等对样品进行了详细的表征。以紫外光光催化降解甲基橙为反应模型评价了样品的光催化性能。结果表明:沉淀法合成的立方晶型Sb2O3纳米晶颗粒小,表现出良好的光催化性能。对立方晶型Sb2O3纳米晶光催化降解甲基橙的原因进行了探讨,并提出了降解甲基橙的反应机理。     

Y2O3:Eu纳米晶的硝基取代苯甲酸配合物固相热解制备和性能

以苯甲酸、邻硝基苯甲酸、间硝基苯甲酸、对硝基苯甲酸、3,5 二硝基苯甲酸等为配体制备了Y3+、Eu3+二元配合物,配合物中Y3+与Eu3+的摩尔比为9：1.利用这些配合物的爆炸式热分解特性通过固相热解反应制备了一系列Y2O3:Eu纳米晶.透射电镜观察,可以看出所得纳米晶呈球形,粒度介于40～60 nm,X射线衍射分析表明实验所得纳米晶属立方晶系,粒径与电镜观察所得结果基本一致；Eu3+的引入并不影响Y2O3的晶相组成；配体类型对纳米晶的结构没有显著影响,不过相对于硝基取代苯甲酸配合物,苯甲酸配合物热解所得Y2O3∶Eu纳米晶团聚严重；退火温度显著影响纳米晶粒度,退火温度高,纳米晶粒度大,反之亦然.荧光光谱测定表明所有Y2O3∶Eu纳米晶具有相似的发光行为,其中以苯甲酸配合物分解所得Y2O3:Eu纳米晶发光性能最为优越.     

纳米Y2O3/钴基合金激光熔覆层的组织

利用5 kW CO2激光器,在Ni基高温合金表面,熔覆纳米稀土氧化物(Y2O3)/钴基合金复合材料,制备了涂层.利用光学显微镜、扫描电镜及透射电镜分析了熔覆层的组织结构.结果表明: 熔覆层的主要相组成为γ-Co,ε-Co,Cr23C6和Y2O3;加入纳米Y2O3,凝固组织由细长的柱状树枝晶转变为较短的树枝晶;纳米Y2O3含量增大至1%时整个断面获得等轴晶组织;纳米Y2O3作为异质形核的核心,细化了组织;纳米Y2O3在熔覆层中分布不均匀,促进了γ-Co向ε-Co的转变;熔覆层的亚结构为堆跺层错.对熔覆层等轴组织形成机制进行了分析.     

Fe3O4@YF3:Eu3+双功能复合颗粒的制备与性能研究

采用直接沉淀法合成了Fe3 O4@ YF3:Eu3核壳结构磁性-荧光性双功能纳米复合颗粒,对其结构和性能进行了表征.XRD分析表明,得到了结晶良好的尖晶石型Fe3 O4纳米晶和正交相的YF3纳米晶.TEM照片表明,双功能复合颗粒具有明显的核壳结构.构成核的Fe3 O4纳米颗粒尺寸在40 ～80nm之间.Fe3 O4@ YF3:Eu3+核壳结构复合纳米颗粒的尺寸约为100 ～250 nm,壳层YF3:Eu3+厚度介于20 ～30 nm之间.EDS分析表明样品由Y,F,Eu,O和Fe元素组成.荧光光谱和磁性测试结果表明,复合颗粒同时具有良好的发光性和较强的磁性,使其在生物医学领域具有潜在的应用.     

超声辐射沉淀法制备纳米γ -MnO2的研究

以KMnO₄和MnSO₄·H₂O为原料，采用超声辐射沉淀法制备出纳米γ-MnO₂粉体，研究了反应物浓度、滴速、超声时间及超声功率等合成条件对粉体的影响，得出了最佳工艺条件。ICP、XRD和TEM分析表明, 施加超声辐射对反应体系有显著影响，超声辐射沉淀法获得了含K量极低，分布均匀，平均晶粒尺寸约10 nm的近球形γ-MnO₂粉体，而未施加超声辐射的普通沉淀法却得到了棒状KMn₈O₁₆粉体。XPS与IR分析表明，两种方法所得粉体中Mn主要以+4价形式存在，而前者具有较多的氧缺位，由于K⁺进入了确定的晶格位置使后者的Mn-O键红外吸收峰明显不同于前者。     

若干物理处理方法对稀土荧光粉Y2O3:Eu3+发光性能的影响

采用物理法对商品化稀土荧光粉Y2O3：Eu^3＋进行改性，考察了真空干燥温度、焙烧温度对其发光性能的影响。SEM和TEM观测结果表明，经过200℃真空干燥后，随着焙烧温度的增加，荧光粉的分散性得到改善，且以纳米颗粒为主（5～85nm）。XRD测量结果表明，随着焙烧温度的增加，Y203：Eu^3＋的结晶度逐渐增加。发射光谱测试结果表明，真空干燥温度为200℃，焙烧温度为1200℃时得到的样品的发光性能较好。     

Yb:Y_2O_3纳米粉体及陶瓷的制备和性能

以Y2O3和Yb2O3为原料,采用柠檬酸溶胶-凝胶法制备了Yb:Y2O3纳米粉体,将该粉体成型后在1500℃烧结7 h获得Yb:Y2O3陶瓷。XRD测试结果表明,Yb:Y2O3纳米粉体的合成温度为800℃。扫描电镜分析表明,Yb:Y2O3粉体的平均直径为40 nm左右。差热-热重分析表明,Yb:Y2O3纳米前驱粉体中柠檬酸和硝酸等在300℃左右分解。荧光光谱分析发现Yb:Y2O3陶瓷的最强荧光发射峰位于1030 nm,是Yb3+的2F7/2-2F5/2谱项导致的荧光发射。     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

γ-Nitro-γ-butyrolacton

γ-Nitro-γ-butyrolactone By oxidation of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) with KMnO₄, besides 3-(1′-nitro-2′-oxocyclohexyl)pripionic acid ( 2 ), the complete hydrolysis product 4-oxononanedioic acid ( 4 ) and the oxidized semi-hydrolysis product 5-(2-nitro-5-oxotetrahydro-2-furyl)pentanoic acid ( 3 ) were formed. The crystalline 3 decomposes at r.t. forming 4 and nitrous gases; its structure was established by X-ray determination.     

Synthesis of γγγ-trifluorocarbonyl compounds

γγγ-Trifluorocarbonyl compounds are easily obtained in a good yield by introduction of the 1,1,1-trifluoroethyl moiety (CF₃-CH₂-) on the -methylene group of a ketone.     

3x-pyrrolizin-3-ones

Condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groups, in the KOH-DMSO system, was used to prepare previously unknown 1-alkylthio-3H pyrrolizin-3-ones. The latter, treated with secondary amines, are readily converted to the corresponding 1-amino derivatives.     

3-H-pyrrolizin-3-ones

Previously unknown 1-alkylthio-3H-pyrrolizin-3-ones have been obtained by the condensation of pyrrole-2-dithiocarboxylates with CH acids containing ester groupings in the KOH-DMSO system. On treating the products with secondary amines they are readily converted into the corresponding 1-amino derivatives.Irkutsk Branch of the Russian Academy of Sciences, Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–924, July, 1996. Original article submitted May 2, 1996.     

Freezing the polarization of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite films

Thin films of methylammonium lead halides, CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, were deposited onto symmetrical microstructured electrode arrays of gold or platinum on Si/SiO₂ wafers. Polarization studies were carried out on perovskite films under vacuum in the dark. For poling, a constant voltage was applied to the samples while the temperature was cycled between 295 K and 4 K. The measured current densities depending on the temperature showed distinct characteristics relating strongly to the crystal phase and the dielectric properties of the perovskite films. Voltage sweeps were carried out at different scan rates at specific temperature intervals after poling. The polarization of the films due to the migration of iodide vacancies in direction of the blocking perovskite/metal interface was frozen almost up to room temperature. Charge carriers were only able to cross the blocking barrier and contribute to the current where the ions have accumulated during poling. All J-V curves showed hysteresis: inverted and regular hysteresis at room temperature and below, respectively. Inverted hysteresis originates from the slow accumulation of ions at the blocking barrier, while regular hysteresis arises from a distortion in the adjacent crystals which will be discussed.     

Synthesis of some derivatives of 3-amino-3-desoxyerythrose and 3-amino-3-desoxy-D-3-erythrose

The synthesis of derivatives of 3-amino-3-deoxy-L-erythrose by LAH or LAD reduction of the oxime of 1,2-O-isopropylidene α-L -glycero-tetros-3-ulofuranose is described.     

K3BiSe3, Rb3BiSe3 und Cs3BiSe3 – Substitutionsvarianten des Th3P4-Typs

K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ – Derivatives of the Th₃P₄ Structure Type The compounds K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃ were synthesized by heating mixtures of Bi₂O₃ and the respective alkalicarbonate in a stream of hydrogen saturated by selenium at 850°C. Thin crystals of the compounds appear red in transmitted light. They crystallize isostructural with Na₃AsS₃, space group P2₁3, lattice constants a = 9.771(5) Å, a = 10.161(3) Å, and a = 10.587(5) Å for K₃BiSe₃, Rb₃BiSe₃, and Cs₃BiSe₃, respectively. The Na₃AsS₃ structure type is a derivative of the Th₃P₄ structure type.