Mg-Cr~(2+)橄揽石、辉石和尖晶石的晶胞参数测定及Cr~(2+)在各晶体结构中的占位

本文用Mg－Cr2+做榄石、辉石、尖晶石的粉晶X射线衍射数据，采取“整体图谱最小二乘Rietveld”方法计算了上述矿物的晶胞参数和摩尔体积，并对Cr2+在各晶体结构中的占位情况进行了研究。结果显示，各矿物的晶胞参数随含Cr2+量的增大而增大。据Vegard定律，推算出各端元组分铬橄榄石（Cr2SiO1）、铬辉石（Cr2SiO2O6）及立方铬尖晶石（Cr3O4）的摩尔体积分别为47．7，68．0，44．9cm3。精化结构参数指示，在橄榄石中，Cr2+随机分配在两个八面体（M1，M2）位置；在辉石中，Cr2+优先选择八面体M2位置；在尖晶石中，Cr2+占置四面体位置。这种晶体内离子分配可从离子半径差别或晶体场稳定能大小得到解释。     

Mg—Cr^2＋橄榄石,辉石和尖晶石的晶胞参数测定及Cr^2＋在各晶体结构…

本文用Ｍｇ－Ｃｒ＾２＋橄榄石、辉石、尖晶石的粉晶Ｘ射线衍射数据，采取“整体图谱最小二乘Ｒｉｅｔｖｅｌｄ”方法计算了上述矿物的晶胞参数和摩尔体积，并对Ｃｒ＾２＋在各晶体结构中的占位情况进行了研究。结果显示，各矿物的晶胞参数随含Ｃｒ＾２＋量的增大而增大。据Ｖｅｇａｒｄ定律，推算出各端元组分铬橄榄石（ＣＦ２ＳｉＯ４）、铬辉石（Ｃｒ２ＳｉＯ２Ｏ６）及立方铬尖晶石（Ｃｒ３Ｏ４）的摩尔体积分别为４７．７，６８     

稀土尖晶石ZnY2O4的软化学合成与表征

本文使用流变相反应法合成草酸盐先驱物,并通过热分解得到ZnY2O4稀土复合氧化物,使用TG,IR和XRD等分析方法研究了ZnY2O4的结构和合成机理,并通过Rietveld分析方法得到产物的结构为尖晶石相关相(图1,表1).     

Cr^2＋在橄榄石,斜方辉石和尖晶石中溶解度的实验研究

为了研究Ｃｒ＾２＋在橄榄石、斜方辉石和尖晶石中的溶解度及其在各相间的分配，在压力为０－２．８８ＧＰａ和温度为１１００－１４５０℃的条件下，于ＭｇＯ－ＳｉＯ２－Ｃｒ－Ｏ体系中完成了一系列实验。实验起始成分由高纯度的ＭｇＯ、ＳｉＯ２、Ｃｒ２Ｏ３和Ｃｒ混合得到。通过Ｃｒ２Ｏ３和Ｃｒ等化学混合得到所需的ＣｒＯ，且加有过量（５０％）的Ｃｒ，使得实验产物和金属Ｃｒ保持平衡。此外，还加入占起始混合物重量１０％的     

尖晶石CoAl2O4中阳离子分布的温度依赖性

本通过Ｘ射线粉末衍射数据的Ｒｉｅｔｖｅｌｄ结构精化法，确定了经过７５０－１２００℃淬火的合成尖晶石ＣｏＡｌ２Ｏ４样品的阳离子分布。其反生参数ｘ随温度７５０－１２００℃相应地从０．１１平滑增加到０．２５（±０．００５），并可用带有ａｃｏ－Ａｌ＝４５．３＋０．５，β＝－１８．３±１．２ｋＪ／ｍｏｌ的一般热力学模型描述。     

第一原理计算过渡金属掺杂尖晶石型LiMn2O4的电子结构

尽管对过渡金属掺杂锰酸锂后放电平台的升高现象有众多实验研究,但对其机理的研究却鲜见报道.采用第一原理的密度泛函理论,计算了过渡金属M(M=Ti、Cr、Fe、Co、Ni、Cu、Zn)掺杂尖晶石型LiMn2O4的电子结构,并以此分析放电平台的升高机理.电子态密度分析发现由于M-3d能带的诱导作用,出现了新的O-2p能带,而锂脱出时获得的电子,主要是由费米能级附近O-2p能带提供的.当过渡金属M由Ti变化到Zn时,M-3d能带逐渐向低能量的方向移动,新的O-2p能带出现的位置也随之下移,当Li脱出时,需要更多的能量才能从低能量的O-2p能带上获得电子,因而体系能够获得较高的嵌入电压.     

高温高压下Mg2SiO4-MgAlO4体系相变的实验研究

采用多顶砧高压实验装置研究了Mg2SiO4-MgAl2O4体系在压力为22 GPa,温度为1550～1750℃条件下的相变,并考查了Al2O3在γ相中的固溶度.结果表明,随着体系中MgAl2O4组分含量的增加,相组合发生了变化,依次为γ相+镁铝硅酸盐固溶体+方镁石→镁铝硅酸盐固溶体+方镁石→镁铝硅酸盐固溶体+方镁石+刚玉固溶体;镁铝硅酸盐固溶体具有石榴子石结构,其化学成分随着体系中共存相的改变而有所变化;Al2O3在γ相中的固溶度很低(其重量百分比＜0.8%),因此,在Mg2SiO4-MgAl2O4体系中Al2O3可能对γ相超尖晶石分解转变的压力不会有很大的影响.     

Li2B4O7—Na2B4O70H2O三元体系25℃相关系及物化性质实验

通过实验研究了Ｌｉ２Ｂ４Ｏ７－Ｎａ２Ｂ４Ｏ７－Ｈ２Ｏ三元体系２５℃相关 溶液的物化性质，其２５℃相图由二条溶解度曲线构成，分别对应于Ｌｉ２Ｂ４Ｏ７．３Ｈ２Ｏ、Ｎａ２Ｂ４Ｏ７．１０Ｈ２Ｏ相区，属简单共饱和型。简要讨论了该体系硼酸盐在水听溶解行为，并用经验公式描述了物有浓度的变化规律。     

2-（2-喹啉偶氮）-1，3-二羟基苯固相萃取光度法测定水中铀

研究了2-(2-喹啉偶氮)-1,3-二羟基苯(QADHB)与铀的显色反应,在TritonX-100和F-存在下,pH7.8的三乙醇胺-HCl缓冲介质中,QADHB与U(Ⅵ)、F-反应生成1∶1∶1紫色三元稳定配合物,配合物的λmax=560nm,ε=7.41×104L·mol-1·cm-1。铀含量在0～2000μg/L内符合比尔定律。环境水样中的铀经磷酸三丁脂萃淋树脂固相萃取柱分离和富集后测定。方法已用于实际样品的测定,分析结果与国标(5-Br-PADAP)法一致,相对标准偏差(n=5)为2.4%～4.7%,回收率为96%～105%。     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x )2SiO4, 0.2 ≤ x ≤ 1.0

 The variation of the oxygen content in olivines, (Fe _x Mg_{1− x} )₂SiO₄, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO₂ and N₂ and, at a few spots at the bottom of the sample stack, also with SiO₂. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe³⁺ ions on M sites and Fe³⁺ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO₂ or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.     

Li2B4O7熔融玻璃-激光剥蚀等离子体质谱法测定水系沉积物国家标准定值样品中微量元素

建立了激光剥蚀等离子体质谱法直接测定Li2B4O7熔融玻璃中微量元素的分析方法。详细讨论了内标元素的选择及Li2B4O7熔融玻璃的均一性、背景空白对分析测定的影响。以Li2B4O7熔融玻璃中低同位素丰度的6Li作内标，水系沉积物国家标准参考物质熔融玻璃建立多元素标准校正曲线，用于标准参考物质及水系沉积物定值样品的分析，测定值与标准值或溶液雾化等离子体质谱结果比较，具有较好的一致性。