Synthesis and characterization of (C5H9C9H6)(2)Yb(THF)(2)(II) (1) and [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2), and ring-opening polymerization of lactones with 1

Reaction of YbI2 with two equivalents of cyclopentylindenyl lithium (C5H9C9H6Li) affords ytterbium(II) substituted indenyl complex (C5H9C9H6)(2)Yb(THF)(2) (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI2 and cyclopentylcyclopentadienyl sodium (C5H9C5H4Na) gives complex [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2) in the presence of a trace amount of O-2, the molecular structure of which comprises two (C5H9C5H4)(2)Yb(THF) bridged by an asymmetric O-2 unit. The O-2 unit and ytterbium atoms define a plane that contains a C-i symmetry center.

SYNTHESIS AND STRUCTURE CHARACTERIZATION OF LANTHANUM [2,2,2]CRYPTATES, [LACL[2,2,2](H2O)]CL-2-CENTER-DOT-H2O AND [LA(CF3SO3)[2,2,2]1(DMF)](CF3SO3)(2)

Two lanthanum(III) [2,2,2]cryptates, [LaCl[2,2,2](H2O)]Cl-2.H2O (1) and [La(CF3SO3)[2,2,2](DMF)] (CF3SO3)(2) (2) have been prepared by the reaction of LaCl3 and La(CF3SO3)(3) with [2,2,2]cryptand, respectively and their crystal structures have been determ

1-(4-fluorophenyl)-2-{4-phenyl-5-[(1H-1,2,4-triazol-1-yl) methyl]-4H-1,2,4-triazol-3-ylsulfanyl}ethanone

The crystal structure of the title compound, C19H15FN6OS, is stabilized by a weak intermolecular C-(HN)-N-... hydrogen-bond interaction.

高Tc超导体R_1Ba_2Cu_3O_(2-x)(R-rare earth)的磁性和超异电性研究

本论文合成了R_1Ba_2Cu_3O_(2-x) (R = La、Nd、Sm、Eu、Gd、Dr、Ho、Er、Tm、Yb)、Y_2Ba_2Cu_3O_(2-x) (x = 0.10～1.17)和Y_1Ba_2Cu_3O_(7-x)S_x (x = 0～2)，并对磁性和超导电性进行了较为系统的研究。R_1Ba_2Cu_3O_(2-x)的磁化率在T > Tc的很宽的温度范围内服从Curic-Weiss定律，求得的有效磁矩略大于理论值，差值与Y_1Ba_2Cu_3O_(2-x)中Cu~(2+)磁矩相近，说明Cu~(2+)的磁矩对体系磁性有额外贡献，这贡献随R~(3+)离子中自旋平行的电子权的增多而增大。其高温下的磁化率CT > 700K)相对Curic-Weiss定律发生较大偏离，这偏离可能的来源有三个：高温下稀土离子发生较大的能级反转效应，高温下结构相变对磁性的影响，高温下氧含量减少造成Cu~(2+)磁矩增大。R_1Ba_2Cu_3O_(2-x)磁化率在T < Tc时也服从Curic-Weiss定律，R~(3+)磁矩是定域的，表明超导与磁性相互独立。互不相关，稀土磁矩与传导电子间无相互作用。用Sr取代R_1Ba_2Cu_3O_(2-x)中的Ba，没能使体系产生磁有序的变化，但却使有效磁矩增大，并完全破坏了样品的超导电性。Sm~(3+)磁化率不服从Curic-Weiss定律，在Sm_1Ba_2Cu_3O_(2-x)中Sm~(3+)显示了典型Van VlccK离子的特性。Y_1Ba_2Cu_3O_(2-x)随氧含量减少发生超导体一半导体一绝缘体的转化，当氧含量由6.90减小至6.49时发生由正交到四方的结构相变。当(7-x) = 5.83时有较多杂质相出现，123相开始分解。样品磁化率均服从Curic-Weiss定律，并随氧含量增大磁化率－温度曲线越来越趋于平缓（直线），当(7-x) = 6.90时磁化率基本不随温度变化，这时Pauli顺磁性占主导地位，这说明氧含量增加定域磁矩减少，求得的有效磁矩Peff随氧含量增大总趋势减小。提出了电子“巡游”的观点，较好地解释了上述现象，并推测出Cu(2)的d电子是离域的，对样品磁矩没有贡献，样品Peff来源于部分Cu(1)的定域Cu~(2+)的磁矩，上述推测被EPR结果证实。正交相Y_1Ba_2Cu_3O_(2-x)的EPR谱显示了中心对称成准立方晶场中Cu~(2+)(d~9, S = 1/2, I = 3/2)的EPR物性。而四方相样品的EPR谱却出现了明显的各向异性，说明观察到的为Cu(1)的EPR信号，由Cu(1)~(2+)的写域磁矩产生。Y_1Ba_2Cu_3O_(2-x)的EPR信号束源于本体相，而非Y_2Cu_2O_5、BaCuO_2、Y_2BaCuO_5等杂质相。各样品EPR信号的自旋浓度远小于1spin/cu，并随氧含量减小而增大，当(7-x) = 6.49、6.40时自旋浓度出现陡增，这时伴随由正交到四方的转化，证明了电子“巡游”观点的正确。用硫部分取代Y_1Ba_2Cu_3O_2g中的氧，当Y_1Ba_2Cu_3O_(2-x)Sx中x = 0.11时Tc = 92.6K，比Y_1Ba_2Cu_3O_(7-x)升高2K，但由于杂质相的存在，ΔTc加宽。其他样品多为半导体和绝缘体。硫取代0，当x = 0.04，0.06，0.11和1.20时磁化率服从Curic-Weiss定律，并且x = 0.87，1.2时分别在230K、240K出现反铁磁有序。其他样品由于Cu被还原为＋1价而变成抗磁性。x = 0.11 (Tc = 92.6K)，EPR谱为正交场中Cu~(2+)的信号。自旋浓度与温度无关。当所有Cu均为Cu~(1+)时，测问的是-s-的EPR信号，而Cu为混合价态(+1和+2时)测问是上述两种信号的叠加。

Synthesis, characterization and electrical properties of solid state electrolyte materials La2-xCaxMo1.7W0.3O9-delta (0 <= x <= 0.2)

The new compounds La2-xCaxMo1.7W0.3O9-delta (0 <= x <= 0.2) in which La3+ substituted with Ca2+ were synthesized by dry-chemistry techniques based on the oxygen Ionic conductor La2Mo1.7W0.3O9. The new series were characterized by X-ray Diffraction (XRD), Raman and X-ray Photoelectron Spectroscopy (XPS) and the electrical conductivity of samples were investigated by AC impedance spectroscopy. The lattice parameters were reduced due to the smaller atomic radius of the Ca2+ compared with that of the La3+. Furthermore, Additional oxygen vacancies were introduced into La2Mo1.7W0.3O9 lattice by substitution, and then the oxygen ionic conductivity was increased. At 550 degrees C, the conductivity increased 89.9%, that is, from 0.79 x 10(-4) S center dot cm(-1) (x=0) to 1.5 X 10(-4)S center dot cm(-1) (x=0.16, 0.2).

Effect of La/Ce ratio on the structure and electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x=0. 1-0.5) hydrogen storage alloys

The effect of La/Ce ratio on the structure and electrochemical characteristics of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys has been studied systematically. The result of the Rietveld analyses shows that, except for small amount of impurity phases including LaNi and LaNi2, all these alloys mainly consist of two phases: the La(La, Mg)(2)Ni-9 phase with the rhombohedral PuNi3-type structure and the LaNi5 phase with the hexagonal CaCU5-type structure. The abundance of the La(La, Mg)(2)Ni-9 phase decreases with increasing cerium content whereas the LaNi5 phase increases with increasing Ce content, moreover, both the a and cell volumes of the two phases decrease with the increase of Ce content. The maximum discharge capacity decreases from 367.5 mAh g(-1) (x = 0.1) to 68.3 mAh g(-1) (x = 0.5) but the cycling life gradually improve. As the discharge current density is 1200 mA g(-1), the HRD increases from 55.4% (x = 0.1) to 67.5% (x = 0.3) and then decreases to 52.1% (x = 0.5). The cell volume reduction with increasing x is detrimental to hydrogen diffusion D and accordingly decreases the low temperature dischargeability of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy electrodes.

Synthesis and X-ray crystal structure of [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2): Mono(cyclopentadienyl)lanthanide complex bearing a C-2-symmetric tetradentate Schiff-base ligand

Cp2SmCl(THF) reacts with 0.5 equivalent disodium salts of trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine give the title complex [(eta(5)-C5H5)Sm(mu-OC20H20N2O)](2)(mu-THF)(THF)(2) (1). X-ray crystal determination shows that the molecule is a dimer, in which two (eta(5)C(5)H(5))Sm(mu-OC20H20N2O) units are connected via a THF oxygen and two bridging oxygen atoms of Schiff base ligands. The average Sm-C distance is 2.78(7) Angstrom, while those of Sm-O (bridging THF oxygen) and Schiff base oxygens are 2.79(3) and 2.43(4) Angstrom; respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

Measurement of polar C-plane and nonpolar A-plane InN/ZnO heterojunctions band offsets by x-ray photoelectron spectroscopy

The valence band offsets of the wurtzite polar C-plane and nonpolar A-plane InN/ZnO heterojunctions are directly determined by x-ray photoelectron spectroscopy to be 1.76 +/- 0.2 eV and 2.20 +/- 0.2 eV. The heterojunctions form in the type-I straddling configuration with a conduction band offsets of 0.84 +/- 0.2 eV and 0.40 +/- 0.2 eV. The difference of valence band offsets of them mainly attributes to the spontaneous polarization effect. Our results show important face dependence for InN/ZnO heterojunctions, and the valence band offset of A-plane heterojunction is more close to the "intrinsic" valence band offset.

取向聚烯烃在单轴拉伸下的结构演变 -同步辐射小角X射线散射研究

典型的结晶聚合物在受到单轴拉伸时，其应力-应变曲线都会经历弹性变形、应变软化、应变硬化以及断裂的四个阶段，在这些过程中，聚合物内部经历了非常复杂的变化：从球晶结构转变成纤维结构最后至分子链解取向和断裂。尽管已经有很多的实验研究结晶聚合物的形变过程，但是对其中的形变机理仍然存在很多争论。本论文的主要思路就是采用取向态的聚合物这一简单的结构来模拟聚合物微观结构在受到外力作用时，在各个阶段的所经历的形貌演变，并基于这些实验数据提出结晶聚合物的形变机理。本文的主要内容包括： 1、选取了预取向的聚丙烯将其在三个不同的方向下拉伸，分别是拉伸方向平行于、垂直于片晶组的法线方向以及与片晶组的法线方向成45角，以模拟处于外力场中球晶内具有代表性的三组片晶的形变情况，希望对球晶结构转变成纤维结构这一塑性形变机理提供进一步的理解。三个实验分别表现出了三种不同的样品内部结构演变过程，综合所有的结果我们可以得出结晶聚合物发生屈服是片晶的塑性形变能力与非晶区弹性形变能力相互作用的结果。 2、 观察冷拉取向的聚乙烯样品在单轴拉伸下的形貌演变。这个过程相当于结晶聚合物成纤后的继续拉伸至断裂的过程。这一实验同时用于模拟研究聚乙烯塑料管材中的慢速裂纹扩展问题。因为聚乙烯裂纹前端是银纹结构即由高度取向的纤维连接裂纹的表面。裂纹的扩展是伴随着银纹中的纤维断裂的过程。实验数据表明了取向聚乙烯内部是由纤维组成的，纤维内部包含着几束由取向的片晶组构成的微纤。在拉伸的过程中由片晶组长周期的增加，微纤的滑移，纤维的滑移协同运动完成了外部的宏观形变。 3、 聚合物在生产加工过程中，样品会不可避免地受到剪切流动的作用。而受到剪切作用后的，聚合物分子大分子链或链段、微晶必然要表现出不同程度的取向，最终对聚合物材料力学性能会产生很重要的影响。因此研究剪切场下聚合物晶体结构的演化对于了解聚合物材料的加工和使用性能是非常重要的。等规聚丙烯在剪切过程中会出现新的晶型晶，我们发现虽然在剪切条件下生成的晶的片晶比聚丙烯中正常的晶要厚，但是实际上却表现出了比晶更好的流动行为。晶的稳定性要比晶的差，具有较低的熔点。因此我们认为片晶的塑性形变的能力除了与片晶厚度相关也与晶体的平衡熔点有关。 综上所述，我们利用同步辐射小角X射线散射手段对取向聚烯烃在单轴拉伸下的行为进行了广泛和深入的研究，发现了一些新现象，发展了文献中原有的理论，得到了单轴拉伸下取向聚乙烯和聚丙烯的形变机理。

In0.2 Ga0.8 As-GaAs复合应力缓冲层上的1.3 μmInAs/GaAs自组织量子点

用光荧光谱和原子力显微镜测试技术系统研究了在2 nm In0.2Ga0.8As和x ML GaAs的复合应力缓冲层上生长的InAs/GaAs自组织量子点的发光特性和表面形貌.采用In0.2Ga0.8As与薄层GaAs复合的应力缓冲层,由于减少了晶格失配度致使量子点密度从约1.7×109 cm-2显著增加到约3.8×109cm-2.同时,复合层也有利于提高量子点中In的组份,使量子点的高宽比增加,促进量子点发光峰红移.对于x=10 ML的样品室温下基态发光峰达到1350 nm.

MBE InGaAs/GaAs外延层晶胞弛豫直接测量的X射线双晶衍射方法

采用了以解理面为衍射基面,直接测量水平弛豫的方法测量了In_xGa_(1-x)As(衬底为GaAs,X-0.1)外延层的应变及其弛豫状态。在以解理面为衍射基面的衍射曲线上清楚地观测到了衬底峰与外延峰的分裂。表明当InGaAs层厚度较厚(-2μm)时，InGaAs外延层与衬底GaAs已处于非共格生长状态，同时发现大失配的InGaAs晶胞并没有完全弛豫恢复到自由状态。其平行于表面法线的晶格参数略大于垂直方向上的晶格参数(△α/α-10~(-3))。并且晶胞在弛豫过程中产生了切向应变。在考虑了切向应变的基础上准确地确定出了InGaAs层的In组分x。