钙钛矿CaTiO_3-Na_(1/2)La_(1/2)TiO_3体系结构和相变的研究

<正>钙钛矿型化合物在地球科学、材料学和物理学等领域有着极其广泛的研究和应用。CaTiO3-Na1/2La1/2TiO3体系的化合物Ca1-2xNaxLaxTiO3(0.0≤x≤0.50)具有典型的ABO3钙钛矿型结构,为A位替代的完全固溶体。端元成分CaTiO3     

钙钛矿-锶钛矿-钠镧钛矿体系化合物晶体化学的研究概况

钙钛矿—锶钛矿—钠镧钛矿三元系是钙钛矿族矿物的典型代表。常温常压下CaTiO3为Pbnm结构，但随温度增高可分别相变为I4／mcm和Pm3m结构；SrTiO3的稳定结构是Pm3m14／mcm相；Na／2Ln1／2TiO3的结构则随Ln代表的元素种类不同而有所差异。三个端员组分在压力下的结构变化均没有明确的结论。在三个二元系中，只有CaTiO3—SrTiO3体系研究较深入，并已给出了T-X相图。本从样品的合成实验及高温和高压原位测量等方面展望钙钛矿型化合物的晶体化学研究及其意义。     

溶胶凝胶法制备（Eu^2＋，Dy^3＋）SrAl2O4

采用无机盐溶胶-凝胶法制备了颗粒均匀的形态为针状的(Eu2+,Dy3+)SrAl2O4纳米粉体.通过TG-DTA分析和X射线衍射和扫描电镜分析方法,对样品进行了微观结构和表面形态的表征.研究了纳米(Eu2+,Dy3+)SrAl2O4粉体在不同烧结温度下固相反应过程和成相规律.实验结果表明,当样品的烧结温度为500 ℃时是单一的Sr(NO3)2晶相;750 ℃左右生成了Sr3Al2O6,并伴有少量SrAl2O4晶体;1 100 ℃是生成了结晶度良好的针状纳米(Eu2+,Dy3+)SrAl2O4粉体.通过计算,样品粉体晶粒平均为80～100 nm.该晶体粒度随烧结温度升高而逐渐变大.     

陕西八卦庙金矿石英标型特征研究

八卦庙金矿的石英可分为3期，即早期近EW向顺层脉、中期NE向节理脉和晚期缓倾斜切脉。X光衍射分析表明，石英的日胞参数、晶胞体积及有关衍射强度比值（I101/I100）和石英的Au的含量相关关系不明显，但总体上有关晶胞参数值较一般标准石英的要大；不同标高石英的晶胞参数表现为脉动式的变化。另外，从成矿早期到晚期；c0/a0和I101/I100值随温度降低而有所降低，石英薄片红外光谱研究结果表明，石英包裹体中H2O的相对光密度D1/D0值除一个样品较小（0.32)外，其斜 均在1.23-4.77，平均2.3143。总体上Au含量较高的石英其H2O和CO2的相对光密度D1/D0和D2/D0值也具相对较高的趋势；并且D1/D0和D2/D0具有密切的正相关关系，相关系数为0858。这种同步增长说明H2O和CO2气液丰富有利于Au的矿化定集，标高相差150 m样品的H2O和CO2的相对光密度值未发生显著变化且无意含Au性较好的信息说明八卦庙金矿深部的矿化前景依然不错。     

高喜马拉雅康布马曲和波曲河流放射成因^87Sr源岩追踪研究

虽然喜马拉雅河流Sr同位素对现代海洋Sr同位素产生了重要影响,但国际上目前对有关喜马拉雅河流Sr同位素异常源岩（如放射成因87Sr的来源）的认识仍存在着较大争议。为此,笔者等对高喜马拉雅河流波曲和康布马曲在中国境内河水主要离子化学和Sr同位素进行了分析研究,对河流放射性87Sr的来源进行了追踪研究。笔者等的研究数据表明,高喜马拉雅康布马曲和波曲河流主要离子水化学主要是受硅酸盐岩风化的影响。青藏高原河流河水TDS和HCO3-主要受岩性控制,片麻岩和花岗岩区河流TDS〈100（mg/L）、HCO3-〈60（mg/L）,沉积岩区河流TDS〉100（mg/L）、HCO3-〉60（mg/L）,除受蒸发盐岩和地下卤水影响的河流外,河水中HCO3-与TDS成正比,但河水中Si与TDS的关系并不明显。高喜马拉雅河流具有高n（87Sr）/n（86Sr）、低Sr的特征,河流Sr是主要来自于中央结晶岩系硅酸盐岩片麻岩和花岗岩的风化,而片麻岩和花岗岩中具有高n（87Sr）/n（86Sr）、低Sr特征的黑云母的风化应是河流放射成因87Sr的主要来源。     

下地幔温压下(Mg, Fe)SiO3钙钛矿的相稳定性

在69～100 GPa冲击压力(估算温度为2600～4300 K)范围内进行了初始样品为(Mg0.92, Fe0.08)SiO3顽火辉石和MgO+SiO2的冲击压缩回收实验。对回收样品进行的X射线衍射(XRD)分析结果表明: 两发顽火辉石回收样品的主相均是单链状结构硅酸盐, 而非钙钛矿结构; 另外, 回收样品中均未观察到氧化物SiO2 和(Mg0.92, Fe0.08)O的XRD特征谱线; 两发MgO+SiO2回收样品中均观察到SiO2和镁橄榄石(Mg2SiO4)而没有氧化物MgO。实验结果表明: 在冲击压缩过程中样品处于钙钛矿结构, 在冲击卸载过程中样品发生了由钙钛矿结构向单链状结构的逆转相变; 在实验的温压范围内, 不可能发生由(Mg0.92, Fe0.08)SiO3向SiO2和(Mg0.92, Fe0.08)O的化学分解相变, 顽火辉石的高压相——钙钛矿结构是稳定的。高压加载或卸载过程引起的晶格畸变导致回收样品和原始样品的谱线差异, 而高压加载导致钙钛矿型(Mg0.92, Fe0.08)SiO3晶格畸变的可能性更大。     

Olgite矿物的合成、发光性能和结构特征

以Na2CO3, BaCO3, SrCO3, NH4H2PO4和Eu2O3为原料,利用高温固相反应法合成了Eu3+离子掺杂的磷锶钡钠石(Ba,Sr)(Na,Sr)2Na(PO4)2粉末样品.用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、傅里叶变换拉曼光谱(FT-Raman)和扫描电镜(SEM)等技术对其物相组成、结构和晶体形貌进行了表征.探讨了不同晶体结构中Sr/Ba比对晶体结构和发光性能的影响.实验通过对Eu3+的发光特点的表征和研究,分别测试了Eu3+离子的室温激发光谱和发射光谱.研究结果表明:(Ba,Sr)(Na,Sr)2Na(PO4)2属简单六方晶系,所有的振动均来自PO43-阴离子团,Eu3+占据非反演中心的格位,该材料中阳离子位置具有高度扰动性的特点.     

洞穴次生碳酸盐沉积的Sr同位素组成研究：历史与前景

对洞穴次生碳酸盐沉积87Sr/86Sr比值的研究进行了回顾,对其潜在的应用前景作了展望。87Sr/86Sr是进行沉积物来源示踪的重要地球化学指标之一。在以往的研究中,根据洞穴次生碳酸盐沉积87Sr/86Sr的变化对一些可能的Sr来源的相对贡献进行了研究,并进一步对其蕴涵的气候环境演化意义进行了探讨。在未来的研究中,示踪物源仍然将是洞穴沉积87Sr/86Sr研究的主要功能。这一指标可能在对地表土壤的化学风化强度及其变化、东亚地区的大气粉尘活动和冬季风演化、岩溶地下水古水文演化研究等方面发挥重要作用。     

河北平原地下水锶同位素形成机理

为了研究河北平原地下水锶同位素的来源与形成机理, 对所采水样进行了分析.研究了87Sr/86Sr比值“时间积累效应”: 随着地下水年龄和埋深的增大而增大; 与地下水中过剩4He_exc呈正相关关系, 与δ18O和δD呈负相关关系.探讨了Sr2+与87Sr/86Sr比值的关系, 将地下水分为3类: (1) 中等Sr2+含量与高87Sr/86Sr比值水(Ⅰ类水); (2) 低Sr2+含量与高87Sr/86Sr比值水(Ⅱ类水); (3) 高Sr2+含量与低87Sr/86Sr比值水(Ⅲ类水), 即热水.通过综合分析认为: (1) 河北平原第四系地下水中的放射成因Sr是由富含Na和Rb的硅酸盐矿物风化作用提供的, 主要矿物为斜长石; (2) 黄骅港热水中的放射成因Sr是由碳酸盐溶解形成的, 87Sr/86Sr比值低, Sr/Na比值大; (3) 补给区地下水是由流经火成岩和变质岩区地下水的侧向补给的, 87Sr/86Sr比值中等.第三系地下水放射成因Sr的来源及形成机理尚须进一步研究.      

钙钛矿型结构亚硝酸盐和氰化物的分子体积

绝大部分的亚硝酸盐和氰化物属于钙钛矿型结构,但有部分化合物为“反”钙钛矿型结构,充填空洞A位的阳离子的拓扑体积为0。阴离子团NO₂^-和CN^-的拓扑体积都近乎常数,分别为41.73ų和40.03ų,标准方差σ_n-1=1.516和σ_n-1=1.25。由此,进一步证明了原来的一套离子拓扑体积数值的普适性。“反”钙钛矿型结构中A位阳离子的平均半径r_A>1.00Å时,三价阳离子会产生扩容效应,其扩容系数大约是其本身拓扑体积的2倍;正钙钛矿型结构中,当A位是由半径较大的Cs⁺充填时,Cs⁺也会产生扩容效应,其扩容系数约为24ų。氰化物中结晶水分子的拓扑体积近乎常数,为24ų或0。     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

Lattice preferred orientation in CaIrO<Subscript>3</Subscript> perovskite and post-perovskite formed by plastic deformation under pressure

Lattice preferred orientations (LPO) developed in perovskite and post-perovskite structured CaIrO₃ were studied using the radial X-ray diffraction technique combined with a diamond anvil cell. Starting materials of each phase were deformed from 0.1 MPa to 6 GPa at room temperature. Only weak LPO was formed in the perovskite phase, whereas strong LPO was formed in the post-perovskite phase with an alignment of the (010) plane perpendicular to the compression axis. The present result suggests that the (010) is a dominant slip plane in the post-perovskite phase and it is in good agreement with the crystallographic prediction, dislocation observations via transmission electron microscopy, and a recent result of simple shear deformation experiment at 1 GPa–1,173 K. However, the present result contrasts markedly from the results on MgGeO₃ and (Mg,Fe)SiO₃, which suggested that the (100) or (110) is a dominant slip plane with respect to the post-perovskite structure. Therefore it is difficult to discuss the behavior of the post-perovskite phase in the Earth’s deep interior based on existing data of MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃. The possible sources of the differences between MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃ are discussed.     

Microstructure and texture formation in extruded lead sulfide (galena)

Lead sulfide (galena) of different purity and grain size was extruded through a round and rectangular die at temperatures between 773 and 923 K. Global and local lattice preferred orientations (here referred to as textures) were measured by neutron and electron back-scattering diffraction. Tension leads to a <100> <111> double fibre texture. Pure shear deformation yields texture components near the ideal face-centered cubic metal brass, copper, Goss and cube positions. The intensity of the components depends on the purity and/or grain size. The microstructure is partially recrystallized. Electron back-scattering diffraction indicates that in tension the <100> and in pure shear the Goss and cube components are associated with dynamic recrystallization. The deformation texture can be qualitatively explained by the full and relaxed constraints Taylor model using slip on {100}<110>, {110}<110> and {111}<110> systems. The texture formation in lead sulfide compares well with that observed for other ionic crystals with the NaCl-structure as well as for face-centered cubic metals with a high stacking fault energy.     

Structure and crystal chemistry of perovskite-type MgSiO3

Synthetic clinoenstatite (MgSiO₃) has been converted to a single phase with the perovskite structure in complete reactions at approx. 300 kbar in experiments that utilize the laser-heated diamond-anvil pressure apparatus. The structure of this phase after quenching was determined by powder X-ray diffraction intensity measurement to be similar to that of the distorted rare-earth, orthoferrite-type, orthorhombic perovskites, but it is suggested that such distortion from ideal cubic perovskite would diminish at high pressure. The unit cell dimensions and density of perovskite-type MgSiO₃ at ambient conditions (1 bar, 25°C) are a=4.780(1) Å, b=4.933(1) Å, c=6.902(1) Å, V=162.75 ų, and ρ=4.098(1) g/cm³. This phase is 3.1% denser than the isochemical oxide mixture [periclase (MgO)+stishovite (SiO₂)]. The small crystal-field stabilization energy of the cation site in the perovskite structure may play an important role in limiting the high-pressure stability field of perovskites that contain transition metal cations. Approximate calculations of the crystal-field effects indicate that perovskite of pure FeSiO₃ composition may become stable at 400–600 kbar; pressures greater than 800 kbar would be required to stabilize CoSiO₃ or NiSiO₃ perovskite.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

Electron microscopy study of domain structure due to phase transitions in natural perovskite

Transmission electron microscopy on natural calcium metatitanate perovskite (dysanalyte) reveals the following twin laws in the orthorhombic (space group Pbnm) phase: reflection twins on the {110} and {112} planes, and 90° rotation twins about the [001] axis (referred to as [001]_90° twin). Single crystals that were heattreated and quenched from above 1585 K exhibit a dramatic change in domain structure compared with the starting material and specimens quenched from T < 1470=" k.=" mutually=" perpendicular=" {110}=" and=">_90° twins are observed throughout the crystal, forming a cross-hatched domain texture. 1/2[001] antiphase domains, which are very rarely observed in the starting material, also become dominant in the crystal. This change in domain structure is interpreted as due to a structural phase transition in perovskite at a temperature below 1585 K. From the point symmetry elements that describe the twin laws and the translational elements that relate the antiphase domains, the most likely phase near 1585 K is tetragonal with space group P4/mbm. These results are consistent with high-temperature powder X-ray diffraction study. On the other hand, density of the {112} twins is increased significantly in the crystal quenched from 1673 K. Twin domains are either bound by mutually perpendicular {110} and (001) walls, or by {112} walls with {110} twin domains within the polygonal {112} domains. Both twin density variation and domain morphology suggest that the crystal may be cubic at this temperature. Microstructure of a single crystal deformed at 1273 K and 3.5 GPa (within the orthorhombic stability field) is morphologically quite distinct from that of the heat-treated specimens. Dislocations dominate the microstructure and often interact with twin domain boundaries.A National Science Foundation Science and Technology Center     

Peierls dislocation modelling in perovskite (CaTiO<Subscript>3</Subscript>): comparison with tausonite (SrTiO<Subscript>3</Subscript>) and MgSiO<Subscript>3</Subscript> perovskite

We present here a numerical modelling study of dislocations in perovskite CaTiO₃. The dislocation core structures and properties are calculated through the Peierls–Nabarro model using the generalized stacking fault (GSF) results as a starting model. The GSF are determined from first-principles calculations using the VASP code. The dislocation properties such as collinear, planar core spreading and Peierls stresses are determined for the following slip systems: [100](010), [100](001), [010](100), [010](001), [001](100), [001](010), and All dislocations exhibit lattice friction, but glide appears to be easier for [100](010) and [010](100). [001](010) and [001](100) exhibit collinear dissociation. Comparing Peierls stresses among tausonite (SrTiO₃), perovskite (CaTiO₃) and MgSiO₃ perovskite demonstrates the strong influence of orthorhombic distortions on lattice friction. However, and despite some quantitative differences, CaTiO₃ appears to be a satisfactory analogue material for MgSiO₃ perovskite as far as dislocation glide is concerned.     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

A new phase transition in MnTiO3: LiNbO3-perovskite structure

The stable polymorph of MnTiO₃ at room temperature and pressure has the ilmenite structure. At high temperatures and pressures, MnTiO₃ ilmenite transforms to a LiNbO₃ structure through a cation reordering process (Ko and Prewitt 1988). Single crystals of both phases have been studied with X-ray diffraction to 5.0 GPa. We have obtained the first experimental verification of the close relationship between the LiNbO₃ and perovskite structures, first postulated by Megaw (1968). MnTiO₃ with the LiNbO₃ structure (MnTiO₃ II) transforms directly to an orthorhombic perovskite structure (MnTiO₃ III) between 2.0 and 3.0 GPa. The transition involves a change of volume of -5%, is reversible and has pronounced hysteresis. Only pressure is required to drive the transition because it involves no breaking of bonds; it simply involves rotation of the [TiO₆] octahedra about their triad axes accompanied by displacement of the Mn cations to the distorted twelve-coordinated sites formed by the rotations. An unusual aspect of this transition is that twinned MnTiO₃ II crystals transform to untwinned MnTiO₃ III crystals with increasing pressure. The twin plane of MnTiO₃ II, , corresponds to the (001) mirror plane of the orthorhombic perovskite structure. MnTiO₃ III examined at 4.5 GPa is very distorted from the ideal cubic perovskite structure. The O(2)-O(2)-O(2) angle describing the tilting in the ab plane is 133.3(7)°, in contrast to 180° for a cubic perovskite and the O(2)-O(2)-O(2) angle describing the tilting in the ac plane is 109.3(4)°, as opposed to 90° in a cubic perovskite.     

Dislocation etch pits in galena

The results of dislocation etch pit studies of naturally and experimentally deformed galena single and polycrystals are presented. The etch pitting is simple, inexpensive, rapid and reveals dislocation substructures similar to those found in metals and ceramics. Both {110} < 1 0 > and {100} < 110 > type slip systems have been found in naturally and experimentally deformed galena.