顽火辉石的高温高压同步辐射研究

 采用同步辐射能量色散X射线衍射技术、激光加热技术和金刚石对顶砧（DAC）高压装置,在温度为2 000 K和压力为23 GPa的范围内,对采自地幔二辉橄榄岩中的顽火斜方辉石,进行了原位的高温高压能量色散X射线衍射（EDXRD）测量。实验结果表明：当压力为15.3 GPa、温度为1 600 K时（相当于地球内部410 km处的地震波不连续界面的温压环境）,顽火斜方辉石转变为橄榄石的β相——瓦兹利石（Wadsleyite）相;继续加温加压至2 000 K、23 GPa时（相当于地球内部670 km处的地震波不连续界面的温压环境）,顽火斜方辉石相变为钛铁矿（Ilmenite）结构和钙钛矿（Perovskite）结构的混和相。实验结果进一步证明,在地幔中存在的两个地震波不连续界面是由橄榄石、顽火斜方辉石等矿物的相变引起的。     

THE CHEMICAL COMPOSITIONS OF MINERALS IN QINGZHEN METEORITE AND ITS GEOCHEMISTRY SIGNIFICANCE

The chemical compositions of silicate minerals, sulphide minerals and metal Fe-Ni in theQingzhen meteorite were measured by the microprobe analyses. Based upon these chemicalcompositions, the cosmochemical behaviour and characteristics of the existing forms of themajor elements in the Qinzhen meteorite have been discussed. These characteristics show thatunder the S-rich, O-poor, and strongly reducing conditions, the light metal elements, such asCa, Mg, K, Na may form sulphide, and metal Fe-Ni may contain Si and P. However, we con-sider that the light metal-sulphide can be stable in the lower mantle and there are some Siand P in the Fe-Ni core. Finally, an earth core-mantle model is established, where the Fe-Ni core contains some Si and P; the lower mantle is composed of Mg-rich silicate, SiO_2 andsulphide; the upper mantle, of silicate and oxide.     

下地幔温压下(Mg,Fe)SiO3钙钛矿的相稳定性——对冲击回收样品的微观分析

 在60~110 GPa冲击压力（估算温度为2 300~4 800 K）范围内进行了5发原始样品为(Mg_0.92,Fe_0.08)SiO₃顽火辉石的冲击压缩回收实验，对回收样品进行的X射线衍射（XRD）和红外吸收光谱（IR）分析结果表明：（1）回收样品的主相均是单链状结构硅酸盐，而非钙钛矿结构；（2）回收样品中均未观察到氧化物SiO₂和(Mg_0.92,Fe_0.08)O的XRD 和IR特征谱线；（3）回收样品的XRD、IR特征谱线变得简略，并发现了与原始样品有某些不同的特征谱线，随冲击压力增加，这种变化趋于明显；（4） 通过对比冲击压力在85 GPa以下和97 GPa以上回收样品的XRD、IR特征谱线，没有观察到明显的新谱线特征出现。结合先前的冲击Hugoniot状态方程实验数据分析，可以认为：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；特别是，在实验的温度压力范围内，不可能发生由(Mg_0.92,Fe_0.08)SiO₃向SiO₂和(Mg_0.92,Fe_0.08)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。回收样品和原始样品的谱线差异可能对应于高压加载或卸载过程引起的某种晶格畸变，而高压加载导致钙钛矿型顽火辉石晶格畸变的可能性更大。这一结果将对下地幔矿物学模型的建立和下地幔地震波探测结果的解释提供基础物理依据。     

Thermoluminescence and defect study of MgSiO3 ceramics

Enstatite (MgSiO₃) ceramic powders were synthesised by a low-temperature initiated self-propagating, gas-producing solution combustion process. The prepared powders were characterised by powder X-ray diffraction, scanning electron microscopy and Brunauer–Emmer–Teller specific surface area measurements. Defect centres induced by radiation were studied using the techniques of thermoluminescence (TL) and electron spin resonance (ESR). A well-resolved glow with peak at 178°C and a shouldered peak at 120°C were observed. Two defect centres were identified by ESR measurements, which were carried out at room temperature, and these were assigned to an O^? ion and F⁺ centre. The O^? ion (hole centre) appears to correlate with the main TL peak at 178°C.     

Preparation of Forsterite by the Geopolymer Technique—Gel Compositions as a Function of pH and Crystalline Phases

Mg-bearing silicate precursor gels have been prepared by mixing 0.74 mol/L sodium metasilicate and 1.48 mol/L magnesium nitrate solutions. Caustic soda solution of 1.0 mol/L concentration was introduced to regulate pH. The magnesium nitrate solution was added dropwise to the sodium silicate solution in equi-volume at various pH values. Raw and heat-treated gels were characterized by XRF, TG-DTA, XRD and FE-SEM. As a result, gel compositions were dependent on pH values of mixing solutions. The pH value yielding stoichiometric forsterite composition, MgO/SiO₂ = 2 was reached at pH 9.3. In addition, this value was pH 8.4 for stoichiometric enstatite composition, MgO/SiO₂ = 1. With decreasing pH from 9.3, the ratio became less than 2 and forsterite and enstatite precipitated by heating the gels. With increasing pH from 9.3, the ratio became more than 2 and forsterite and periclase precipitated by heating the gels. DTA curves showed a characteristic exothermic peak centered at 700–900^∘C, indicating relatively low temperature formation of crystalline phases due to the presence of polycondensed frame works of silicates in the precursor gels.     

Differential thermal study of Mg-bearing clays from saline lakes of Southern Tunisia

Clays high in Mg content occur frequently in the high saline environment of salt lakes in southern Tunisia. The DTA curves of these clays show a striking endothermic-exothermic reaction in the temperature range of 800–820°C. A strong correlation is observed between the intensity of these coupled reactions and the Mg content of the initial clay sample. The initial endothermic reaction is interpreted as the melting/dehydroxylation of the Mg-bearing smectites. The subsequent exothermic peak is interpreted as caused by the crystallisation of the new Mg-silicate phase enstatite. Therefore, the DTA is considered as a suitable method for the identification and relative quantification of high Mg clay minerals (e.g. trioctahedral smectites). Variations of the Mg content of the studied samples were well detectable by means of DTA, disclosing a distinct distribution pattern of the salt lake clays. Clues to bulk chemical composition of the initial clay assemblage can also be found in the results of the X-ray analysis of the firing products.     

高压下顽火辉石的相态用其地球物理意义

利用Birch-Murnahan有限应变状态方程和Gru neisen　状态方程,计算了钙钛矿型((Mgo. 86Fe     

Aqueous Syntheses of Forsterite (Mg2SiO4) and Enstatite (MgSiO3)

Forsterite MgSiO₄ and enstatite MgSiO₃ were synthesized by two different aqueous processes. TEOS was directly hydrolyzed in aqueous solutions of magnesium nitrate, giving solutions of magnesium nitrate and silicic acid. For the first process these solutions were spray-dried and the powders heat treated to decompose the nitrate; and for the second one they were precipitated in a solution of ethylenediamine as a base, the resulting precipitate was filtered, washed and dried. Spray-dried or precipitated, no specific thermal event was detected by thermal analysis for the crystallization of forsterite (500–1000°C) while a strong and sharp exothermic peak traduced the crystallization of enstatite at 800°C. Very minor secondary phases could be detected by X-ray diffraction up to 1200°C for the spray-dried powders, while the precipitated powders presented a higher chemical homogeneity, but much care had to be taken for a quantitative precipitation. As some minor secondary phases like SiO₂ or some polymorphs of MgSiO₃ could be not detected by XRD up to 1300°C, higher thermal treatments were necessary to control the purity or the desired phase.     

Effect of interlayer cations on high-temperature phases of vermiculite

Static and dynamic heating of vermiculite samples from Santa Olalla, Huelva, Spain, saturated with different cations, i.e. Na⁺, Cs⁺, NH₄ ⁺, Mg²⁺, Ca²⁺, Ba²⁺ and Al³⁺, have been studied. The characterization of the phases formed during heating has been carried out by X-ray diffraction. The phases formed depend on the cation present in the interlamellar position and the heating process. The phases identified in the vermiculite samples saturated with different cations and heated at different temperatures are the following: enstatite, forsterite, spinel, cordierite, anorthite, pollucite, nepheline, coesite, celsian and others various mixed silicates; also some dehydrated and amorphous phases have been observed. On static heating, at the maximum temperature reached in this work, the phases formed appear mixed with a glassy phase.     

高压下天然顽火辉石能量色散X射线粉末衍射研究

 在北京同步辐射装置（BSRF）高压站对采自于河北大麻坪的天然顽火辉石,在室温高压（0~31.64 GPa）下,利用金刚石压腔装置（DAC）,进行了能量色散X射线粉末衍射（EDXD）原位测量,得到了顽火辉石在不同压力下的衍射图谱,并利用UnitCell软件进行解谱,获得了其晶胞参数a、b、c和晶胞体积V及其随压力的变化,最后利用Murnaghan等温方程得到了天然顽火辉石的体积模量K_T(0)=172 GPa、压缩系数及p-V状态方程,发现沿a、b、c三方向的压缩系数存在明显的各向异性,结果与斜方辉石的弹性波速各向异性完全一致。