微观结构对溶胶-凝胶法合成的La_(0.67)Sr_(0.33)MnO_3电磁性能影响

采用溶胶-凝胶法制备了不同烧结温度的钙钛矿类锰氧化物La0.67Sr0.33MnO3样品。实验结果表明,在1573 K以上烧结的样品,晶粒出现异常长大,晶界效应明显。随着烧结温度的提高,磁化强度逐渐增大,但样品的居里温度基本不变。此外,在1173和1573 K温度下烧结的样品,均出现了低于居里温度的金属-半导体导电行为转变。在合适的烧结条件下,可以观察到隧道磁电阻(TMR)和超大磁电阻(CMR)2种磁电阻效应。实验表明,自旋电子的输运,不仅与样品平均粒径的大小和密度有关,而且与晶界的微观结构有密切关系。

Synthesis, reactive mechanism and thermal stability of W1-xAlxC (x=0.33, 0.5, 0.75, 0.86) nanocrystalline

W1-xAlxC (x = 0.33, 0.50, 0.75, 0.86) solid solutions have been synthesized directly by ball-milling tungsten powder, aluminum powder and activated carbon. The structural development of W0.5Al0.5C phase with the milling times up to 160 h has been followed using X-ray diffraction. X-ray photoelectron spectra demonstrate that Al atom takes the place of W. High temperature annealing experiment reveals that Al is stable in hexagonal structure to 1873 K. Transmission electron microscopy image shows that the grain size of the prepared powders is about 5 nm.

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)(x) (x=2.5-5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) (x) (x=2.5-5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5-3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0-5.0 is LaNi(5)phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9 phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I-0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.

Preparation, patterning and luminescent properties of oxyapatite La-9.33(SiO6)(4)O-2 : A (A = Eu3+, Tb3+, Ce3+) phosphor films by sol-gel soft lithography

Silicate oxyapatite La-9.33 (SiO6)(4)O-2:A (A = Eu3+, Tb3+ and/or Ce3+) phosphor films and their patterning were fabricated by a sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, atomic force microscopy, optical microscopy and photoluminescence spectra, as well as lifetimes, were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800degreesC and the crystallinity increased with the increase in annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of rodlike grains with a size between 150 and 210 nm. Patterned thin films with different bandwidths (20, 50 mum) were obtained by the micromoulding in capillaries technique. The doped rare earth ions (Eu3+, Tb3+ and Ce3+) showed their characteristic emission in crystalline La-9.33(SiO6)(4)O-2 phosphor films, i.e. Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+ D-5(3,4)-F-7(J) (J = 3, 4, 5, 6) and Ce3+ 5d (D-2)-4f (F-2(2/5), F-2(2/7)) emissions, respectively. Both the lifetimes and PL intensity of the Eu3+, Tb3+ ions increased with increasing annealing temperature from 800 to 1100 degreesC, and the optimum concentrations for Eu3+, Tb3+ were determined to be 9 and 7 mol% of La3+ in La-9.33(SiO6)(4)O-2 films, respectively. An energy transfer from Ce3+ to Tb3+ was observed in the La-9.33(SiO6)(4)O-2:Ce, Tb phosphor films, and the energy transfer efficiency was estimated as a function of Tb3+ concentration.

α-B-Keggin型杂多化合物K_5H[Co_4(VW_9O_(33))_2]·5H_2O的合成和结构

合成了新化合物K_5H[Co_4(VW_9O_(33))·5H_2O,并运用IR,UV-ViS,DTA和单晶X射线衍射对其结构进行了表征.测定结果证实标题化合物具有α-B-Keggin型结构,两个(VW_9O_(33)~(7-)结构单元由四个Co(Ⅱ)O_6 八面体连接.杂多化合物属单斜晶系P2_(1/n),a=1.2307(3)nm,b=2.1250(4)nm,c=1.5817(3)nm,β=91.86(3)°,V=4.1343(14)nm~3,R=0.0895,R_w=0.2180.

Ce~（3＋），Tb~（3＋）在Al_4B_2O_9和Al_（18）B_4O_（33）基质中的发光

采用固相反应法在Ａｌ２Ｏ３－Ｂ２Ｏ３体系中合成了Ａｌ４Ｂ２Ｏ９和Ａｌ１８Ｂ４Ｏ３３两个相关化合物，测定了在两种基质中Ｃｅ３＋，Ｔｂ３＋和Ｃｅ３＋－Ｔｂ３＋的光谱，观察到在两种基质中Ｃｅ３＋的光谱相似，Ｃｅ３＋的发射峰位置在Ａｌ１８Ｂ４Ｏ３３中比Ａｌ４Ｂ２Ｏ９稍有红移。实验表明，Ａｌ１８Ｂ４Ｏ３３将是一种好的发光基质

n-C_(16)H_(33)NH_3X和(n-C_(16)H_(33)NH_3)_2MX_4的红外光谱研究

在室温和液氮温度下研究了(n-C_(16)H_(33)NH_3)_2MX_4(简称C_(16)MX)及其相应化合物n-C_(16)H_(33)NH_3X(简称C_(16)X)于4000～50cm~(-1)范围的红外光谱。结果表明,它们都形成N-H…X型氢键,氢键强度是C_(16)X大于C_(16)MX。后者氢键的强度是按Cl>Br>I的顺序递减。C_(16)MX的光谱性质可按金属离子性质分为Cu~(2+)(Cu~(2+)、Cd~(2+)、Mn~(2+))和Zn~(2+)(Zn~(2+)、Co~(2+))两组,阴离子配位多面体的形状对其光谱性质有明显影响。还比较了室温与低温下的远红外光谱,证明了M—X键是离子键。

中国近海和西北太平洋温跃层时空变化分析、模拟及预报

温度跃层是反映海洋温度场的重要物理特性指标，对水下通讯、潜艇活动及渔业养殖、捕捞等有重要影响。本文利用中国科学院海洋研究所“中国海洋科学数据库”在中国近海及西北太平洋（110ºE-140ºE,10ºN-40ºN）的多年历史资料（1930-2002年，510143站次），基于一种改进的温跃层判定方法，分析了该海域温跃层特征量的时空分布状况。同时利用Princeton Ocean Model(POM)，对中国近海，特别是东南沿海的水文结构进行了模拟，研究了海洋水文环境对逆温跃层的影响。最后根据历史海温观测资料，利用EOF分解统计技术，提出了一种适于我国近海及毗邻海域，基于现场有限层实测海温数据，快速重构海洋水温垂直结构的统计预报方法，以达到对现场温跃层的快速估计。 历史资料分析结果表明，受太阳辐射和风应力的影响，20°N以北研究海域，温跃层季节变化明显，夏季温跃层最浅、最强，冬季相反，温跃层厚度的相位明显滞后于其他变量，其在春季最薄、秋季最厚。12月份到翌年3月份，渤、黄及东海西岸，呈无跃层结构，西北太平洋部分海域从1月到3月份，也基本无跃层结构。在黄海西和东岸以及台湾海峡附近的浅滩海域，由于风力搅拌和潮混合作用，温跃层出现概率常年较低。夏季，海水层化现象在近海陆架海域得到了加强，陆架海域温跃层强度季节性变化幅度(0.31°C/m)明显大于深水区(约0.05°C/m)，而前者温跃层深度和厚度的季节性变化幅度小于后者。20°N以南研究海域，温跃层季节变化不明显。逆温跃层主要出现在冬、春季节（10月-翌年5月）。受长江冲淡水和台湾暖流的影响，东南沿海区域逆温跃层持续时间最长，出现概率最大，而在山东半岛北及东沿岸、朝鲜半岛西及北岸，逆温跃层消长过程似乎和黄海暖流有关。多温跃层结构常年出现于北赤道流及对马暖流区。在黑潮入侵黄、东、南海的区域，多温跃层呈现明显不同的季节变化。在黄海中部，春季多温跃层发生概率高于夏季和秋季，在东海西部，多跃层主要出现在夏季，在南海北部，冬季和春季多温跃层发生概率大于夏季和秋季。这些变化可能主要受海表面温度变化和风力驱动的表层流的影响。 利用Princeton Ocean Model(POM)，对中国东南沿海逆温跃层结构进行了模拟，模拟结果显示，长江冲淡水的季节性变化以及夏季转向与实际结果符合较好，基本再现了渤、黄、东海海域主要的环流、温盐场以及逆温跃层的分布特征和季节变化。通过数值实验发现，若无长江、黄河淡水输入，则在整个研究海域基本无逆温跃层出现，因此陆源淡水可能是河口附近逆温跃层出现的基本因素之一。长江以及暖流（黑潮和台湾暖流）流量的增加，均可在不同程度上使逆温跃层出现概率及强度、深度和厚度增加，且暖流的影响更加明显。长江对东南沿海逆温跃层的出现，特别是秋季到冬季初期，有明显的影响，使长江口海域逆温跃层位置偏向东南。暖流对于中国东南沿海的逆温跃层结构，特别是初春时期，有较大影响，使长江口海域的逆温跃层位置向东北偏移。 通过对温跃层长期变化分析得出，黄海冷水团区域，夏季温跃层强度存在3.8年左右的年际变化及18.9年左右的年代际变化，此变化可能主要表现为对当年夏季和前冬东亚地区大气气温的热力响应。东海冷涡区域，夏季温跃层强度存在3.7年的年际变化，在El Nino年为正的强度异常，其可能主要受局地气旋式大气环流变异所影响。谱分析同时表明，该海域夏季温跃层强度还存在33.2年的年代际变化，上世纪70年代中期，温跃层强度由弱转强，而此变化可能与黑潮流量的年代际变化有关。 海洋水温垂直结构的统计预报结果显示，EOF分解的前四个主分量即能够解释原空间点温度距平总方差的95%以上，以海洋表层附近观测资料求解的特征系数推断温度垂直结构分布的结果最稳定。利用东海陆架区、南海深水区和台湾周边海域三个不同区域的实测CTD样本廓线资料，对重构模型的检验结果表明，重构与实测廓线的相关程度超过95%的置信水平。三个区重构与实测温度廓线值的平均误差分别为0.69℃，0.52℃，1.18℃，平均重构廓线误差小于平均气候偏差，统计模式可以很好的估算温度廓线垂直结构。东海陆架海区温度垂直重构廓线与CTD观测廓线获得的温跃层结果对比表明，重构温跃层上界、下界深度和强度的平均绝对误差分别为1.51m、1.36m和0.17℃/m，它们的平均相对误差分别为24.7%、8.9%和22.6%，虽然温跃层深度和强度的平均相对误差较大，但其绝对误差量值较小。而在南海海区，模型重构温跃层上界、下界和强度的平均绝对预报误差分别为4.1m、27.7m和0.007℃/m，它们的平均相对误差分别为16.1%、16.8%和9.5%，重构温跃层各特征值的平均相对误差都在20%以内。虽然南海区温跃层下界深度平均绝对预报误差较大，但相对于温跃层下界深度的空间尺度变化而言（平均温跃层下界深度为168m），平均相对误差仅为16.8%。因此说模型重构的温度廓线可以达到对我国陆架海域、深水区温跃层的较好估算。 基于对历史水文温度廓线观测资料的分析及自主温跃层统计预报模型，研制了实时可利用微机简单、快捷地进行温跃层估算及查询的可视化系统，这是迄今进行大范围海域温跃层统计与实时预报研究的较系统成果。

文33块沙二下段油藏动态模型及剩余油预测

By applying synthetically multi-subject theories, methods and technology, such as petroleum geology, sedimentology, seep mechanics, geochemistry, geophysics and so on; and by making full use of computer; combining quantity and quality, macroscopic and microscopic, intensive static and active description, comprehensive studying and physical modeling, 3 dimension and 4 dimension description; the paper took Wen-33 block of Zhongyuan oil field as an example; and studied reservoir macroscopic and microscopic parameter changing rule and evolve mechanics in different water-blood stage. The reservoir dynamic model and remaining-oil distribution mode was established, and several results were achieved as follows: (1) Three types of parameter gaining, optimizing and whole data body of Wen33th reservoir were established. Strata framework, structure framework, reservoir types and distribution of Wen33th reservoir were discussed. Reservoir genesis types, space distribution law and evolve rule of Wen33th reservoir were explained. 4D dynamic model of macroscopic parameter of reservoir flow dynamic geologic function of Wen33th reservoir was established. The macroscopic remaining-oil distribution and control factor was revealed. The models of the microscopic matrix field, pore-throat network field, fluid field, clay mineral field of Wen-33 block were established. The characters, changing rules and controlled factors in different water stage were revealed. The evolve rule and mechanics of petroleum fluid field in Wen-33 block reservoir were revealed. Macroscopic and microscopic remaining oil distribution mode of Wen-33 block were established. Seven types, namely 12 shapes of dynamic model of microscopic remaining oil were discussed, and the distribution of mover remaining oil was predicted. Emulation model: mathematical model and prediction model of Wen-33 block were established. The changing mechanics of reservoir parameter and distribution of remaining-oil were predicted. Firstly, the paper putting forward that the dynamic geologic function of petroleum development is the factor of controlling remaining-oil, which is the main factor leading to matrix field, network field, clay mineral field, fluid field, physic and chemical field, stress field and fluid field forming and evolving. (10) A set of theories, methods and technologies of investigating, describing, characterizing and predicting complex fault-block petroleum were developed.