高压下天然菱铁矿的压缩性和电子结构研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对天然菱铁矿的压缩性和电子结构进行了原位X射线衍射(XRD)和X射线吸收近边结构谱(XANES)测试研究。在室温下随着压力逐渐升高至50.2 GPa,菱铁矿保持方解石型结构不变,但是逐渐向Na Cl型结构转变;刚性[CO3]2-基团平行于ab-平面定向排列使c轴的压缩性大于a轴。菱铁矿在44.6~47.1 GPa之间发生电子由高自旋态(HS)向低自旋态(LS)的转变,表现为体积塌陷8%。HS菱铁矿的等温状态方程参数为K0=112(5)GPa和K'0=4.6(3)。首次采用XANES技术对菱铁矿中Fe2+的电子结构进行了研究,结果表明:随着压力升高至37.3 GPa,Fe2+的配位和局域对称并未发生明显变化;此后电子结构开始转变,Fe2+的3d轨道分裂能降低,电子跃迁概率增大,呈现LS特性。     

高压下白云石的原位拉曼光谱研究

利用热液金刚石压腔研究了白云石在温度298 K、压力100～1000 MPa下C-O键弯曲振动峰V1097的拉曼变化特征.结果表明,在实验的压力范围内白云石稳定,其拉曼位移和压力具有很好的线性关系,拟合后得出压力与白云石1097 cm-1拉曼线频率位移的关系为:P=143.47(△Vp)1097 102.67(1097＜Vp＜1103).因此白云石非常适合作为热液金刚石压腔的压标.     

透视石的原位高压单晶X射线衍射研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对透视石进行了室温下的原位高压单晶X射线衍射研究。实验的最高压力为11.7 GPa,在实验压力范围内,未观察到透视石发生相变。随着压力的升高,晶胞体积逐步被压缩,体积压缩率符合三阶Birch-Murnaghan状态方程,拟合获得体模量K0为114.6(5.3)GPa。压力低于9.3 GPa时,c轴的压缩率大于a轴;在9.3~11.7 GPa压力范围内,限制于透视石结构中的水分子在高压下会阻碍硅氧四面体六元环沿c轴方向的扭曲变形,导致c轴的抗压性增强,最终a轴与c轴的被压缩程度趋于一致。通过分析多种含水环状硅酸盐矿物的高压行为,发现高压下结构中水的存在形式对含水环状硅酸盐矿物的弹性性质有重要的影响。     

天然翡翠与染色翡翠鉴定方法研究

采用电子探针、X射线衍射仪、激光拉曼光谱仪、红外光谱仪对天然翡翠和染色翡翠进行综合对比研究,结果表明,X射线多晶衍射分析天然翡翠和染色翡翠的主成分均为硬玉;电子探针分析虽未检出染色翡翠中的致色元素,但天然翡翠和染色翡翠的背散射图像截然不同;经拉曼分析,染色翡翠则出现有机染料相似的荧光背景;红外光谱分析,染色翡翠在2800～3100cm^-1范围内出现强烈的吸收峰。因此采用多种方法的测试对比研究,可较准确的区分天然翡翠与染色翡翠,提供客观、公正的鉴定结果。     

高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究.在压力0.1 MPa～837.9 MPa和温度16～200 ℃条件下通过系列实验对相变的过程进行了原位光谱分析.与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现.通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为P(MPa)=19.56·T(℃)-2926.5.     

天然金刚石孪晶的X射线衍射与形貌研究

本文利用X射线衍射和形貌术方法研究了辽南天然金刚石孪晶体。发现晶体中存在有孪晶界、位错、生长带和亚结构等多种缺陷。文中对部分位错进行了详细讨论,并确定其特征量;同时还分析各种缺陷的空间分布特点及其与孪晶界面的关系。     

蓝柱石的高温X射线衍射、差热-热重分析、偏振红外光谱和高压拉曼光谱研究

通过高温X射线衍射(XRD)、差热-热重分析、偏振红外光谱和高压拉曼光谱研究了江西大余的蓝柱石的热膨胀行为、稳定性、羟基峰在(010)面上的强度变化及其常温高压拉曼光谱特征。结果表明,蓝柱石在1273K完全非晶化,其热膨胀系数αV为1.2(1)×10-5+0.16(1)T×10-9/K。蓝柱石在750K开始发生分解反应,最大的反应速率发生在1266K。在蓝柱石的(010)面上,羟基吸收峰在光的偏振方向与c轴夹角为70°和250°时最强,在光的偏振方向与c轴夹角为160°和340°时最弱。在常压至12.3GPa的压力范围内,蓝柱石没有发生相变。通过高压拉曼光谱计算得到了蓝柱石的mode Grüneisen参数的算术平均值为0.52(2)、thermal Grüneisen参数为0.64(2)。另外,根据Grüneisen关系式可以求得thermal Grüneisen参数,其值为0.70(6)。     

金刚石压腔结合拉曼光谱技术进行氧同位素分馏的实验研究

应用水热金刚石压腔结合拉曼光谱技术进行石英和方解石间氧同位素的分馏研究。金刚石压腔装置实现体系的高温高压条件,重氧水为提供18O的中间介质。首先给体系加压至500 MPa左右,然后升温至300℃使石英、方解石发生部分溶解,随后快速降至常温使溶解部分重新结晶,从而使矿物和重氧水之间发生同位素交换。拉曼光谱中,物质特征峰的峰强度比值与相应物质的量的比值呈线性相关,结合同位素分馏系数公式计算得出300℃时石英、方解石之间的氧同位素分馏系数为1.0016。此方法操作简便,实验过程采用原位测量方法,不破坏样品,避免了污染,提高了实验精度。实验数据的准确度证明了金刚石压腔结合拉曼光谱法进行稳定同位素分馏的实验研究是可行的。     

天然文石-方解石的高温相变及热膨胀性质

利用高温粉末X射线衍射研究了高纯地质成因文石从室温到1 073 K的相变过程以及文石和方解石的热膨胀性质,并分析了地质成因与生物成因文石的差异和影响因素。结果表明:斜方晶系的文石在693～733 K转变为三方晶系的方解石,相变临界温度为723 K,摩尔体积增加5.97%;文石在300～663 K的体积热膨胀系数α(V)(10-5/K)随绝对温度T(K)的变化规律为:α(V)=3.59(79)+7.17(170)×10-3T,文石的热膨胀具有强烈的各向异性[轴向热膨胀系数α(c)α(b)α(a)];方解石在733～973 K的热膨胀系数α(10-5/K)为:α(V)=3.78(25),α(a)=-0.27(2),α(c)=4.31(29),a轴具有负热膨胀。生物成因的文石相变温度比合成和地质成因文石低60～140 K,粉末状文石相变温度低于单晶和未被破坏的整块文石;粉末状的生物成因文石和方解石与非生物成因的文石和方解石的热膨胀系数接近,然而整块的生物成因的文石有更小的热膨胀系数。     

钦-杭带南段坡仔营斑岩型钼矿中黄铁矿微组构及其标型意义

坡仔营钼矿是钦-杭成矿带南段最重要斑岩型矿床之一。该矿床发育典型"中心式面型蚀变"和A、B和D三种类型矿化脉。为了加深对其成矿过程的认识,本研究选取不同矿脉中黄铁矿,通过扫描电镜（SEM）、X射线粉晶衍射（XRD）和激光拉曼光谱（Raman）,研究其微组构标型特征,以期反演成矿过程的热力学及动力学信息。SEM结果显示,A脉内黄铁矿较少,呈100~200μm半自形-他形,籽晶呈扁平乳滴状;B脉黄铁矿强烈发育,呈500~1000μm自形-半自形,籽晶呈近椭圆形层状;D脉内黄铁矿呈立方体产出,粒度10~20mm左右,三组相互垂直晶纹发育,籽晶棱角状线形展布。A脉→B脉→D脉中黄铁矿粒度逐渐变大,籽晶更加规则,指示成矿早期至晚期,黄铁矿结晶速度逐渐变缓,成生环境趋于稳定。XRD结果展示,各样品谱线均发育着多组黄铁矿特征峰,但其强峰发育存在差异。A脉最强峰为28.5°,次强峰37.1°;B脉和D脉相应峰位分别为37.1°、33.1°和33.1°、56.3°。衍射峰型特征表明,A脉样品晶形应以（1 1 1）面组成的正八面体单形为主,其次为（2 1 0）晶面组成的五角十二面体,其成生温度应大于300度;B脉样品应以（2 1 0）组成的五角十二面体单形为主,其次为（1 0 0）晶面组成的立方体单形,形成温度应介于200~300℃之间或略大;D脉样品主要以（1 0 0）晶面组成的立方体为主,其形成温度应小于200℃。Raman光谱揭示,A脉样品的ν_Eg=348.0~350.7cm^-1、ν_Ag=385.2~386.5cm^-1、ν_Tg=441.9~422.8cm^-1,与之相比,B脉和D脉的对应值分别向低频偏移2~6cm^-1和5~14cm^-1;A脉样品的散射强度I_Eg=388.8~745.5、I_Ag=1532.8~2071.8、I_Tg=238.9~254.4,而B及D脉样品的散射强度依次明显增强。自A脉→B脉→D脉,拉曼位移向低频偏移,散射强度依次增强,指示三者的成生压力依次降低。本研究认为,坡仔营斑岩型钼矿的成生早期为一个高温、高压岩浆热液活动为主阶段,随着成矿温度、压力的降低,成矿系统氧逸度逐渐降低,硫及金属元素逐步转变为金属硫化物形式而成矿。     

金刚石压腔（DAC）技术及其在地球科学中的应用

近几十年来金刚石压腔（DAC）技术被广泛应用于高温高压实验研究领域,它可以达到550 GPa的压力和6 000 K的温度。与其他静高压实验技术（大压力机、高压釜等）相比,金刚石压腔具有独特的优势,它不仅可以进行极端温压条件下物质的结构性质、相变及状态方程等研究,而且可以原位观测整个实验过程。文中简述了金刚石压腔装置的结构及温压测量方法,然后分别从物质相变、矿物溶解度、流体性质和组成、油气成因、稳定同位素分馏系数和布里渊声学测量等方面简要介绍了金刚石压腔技术在地球科学中的研究进展。随着实验技术的不断发展和更新,金刚石压腔技术将具有更广阔的应用前景。     

Raman study of radiation-damaged zircon under hydrostatic compression

Pressure-induced changes of Raman band parameters of four natural, gem-quality zircon samples with different degrees of self-irradiation damage, and synthetic ZrSiO₄ without radiation damage, have been studied under hydrostatic compression in a diamond anvil cell up to ~10 GPa. Radiation-damaged zircon shows similar up-shifts of internal SiO₄ stretching modes at elevated pressures as non-damaged ZrSiO₄. Only minor changes of band-widths were observed in all cases. This makes it possible to estimate the degree of radiation damage from the width of the ν₃(SiO₄) band of zircon inclusions in situ, almost independent from potential “fossilized pressures” or compressive strain acting on the inclusions. An application is the non-destructive analysis of gemstones such as corundum or spinel: broadened Raman bands are a reliable indicator of self-irradiation damage in zircon inclusions, whose presence allows one to exclude artificial color enhancement by high-temperature treatment of the specimen.     

Structural investigations of (Ca,Sr)ZrO<Subscript>3</Subscript> and Ca(Sn,Zr)O<Subscript>3</Subscript> perovskite compounds

(Ca _x ,Sr_1?x )ZrO₃ and Ca(Sn _y ,Zr_1-y )O₃ solid solutions were synthesized by solid-state reaction at high temperature before to be studied by powder X-ray diffraction and Raman Spectroscopy. Diffraction data allow the distortion of the ABO₃ perovskite structure to be investigated according to cations substitution on A and B-sites. It is shown that distortion, characterized by Φ, the tilt angle of BO₆ octahedra, slightly increases with decreasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds and strongly decreases with decreasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds. Such results are discussed in view of the relative A and B cation sizes. Raman data show that vibrational spectra are strongly affected by the cation substitution on A-site; the frequencies of most vibrational modes increase with increasing x content in (Ca _x ,Sr_1?x )ZrO₃ compounds, i.e. with the decreasing mean size of the A-cation; the upper shift is observed for the 358 cm^?1 mode (?ν/?r = ?60.1 cm^?1/Å). On the other hand, the cation substitution on B-sites, slightly affect the spectra; it is shown that in most cases, the frequency of vibrational modes increases with increasing y content in Ca(Sn _y ,Zr_1?y )O₃ compounds, i.e. with the decreasing mean size of the B-cation, but that two modes (287 and 358 cm^?1) behave differently: their frequencies decrease with the decreasing mean size of the B-cation, with a shift respectively equal to +314 and +162 cm^?1/Å. Such results could be used to predict the location of different elements such as trivalent cations or radwaste elements on A- or B-site, in the perovskite structure.     

Phase transition and compression behavior of gibbsite under high-pressure

In situ high-pressure synchrotron X-ray diffraction and infrared absorption experiments for gibbsite were performed at room temperature up to 53 and 25 GPa, respectively. A phase transition was confirmed at about 2.5 GPa. The high-pressure phase is indexed as an orthorhombic structure, rather than a triclinic structure as reported in previous studies. The compressibility of gibbsite and its high-pressure polymorph were studied, and their bulk moduli K₀ were determined to be 49 and 75 GPa, respectively with K₀ as 4. The in situ high-pressure infrared absorption spectra revealed the gradual disordering of hydrogen substructure above 15 GPa in quasihydrostatic compression.     

High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Elastic constants of single-crystal Pt measured up to 20 GPa based on inelastic X-ray scattering: Implication for the establishment of an equation of state

Phonon velocities and densities for Pt were measured based on inelastic X-ray scattering from ambient pressure to 20 GPa in order to independently determine its equation of state (EOS). Phonon velocities were determined with sine dispersion relations. C_ij values were obtained by fitting phonon velocities and densities to the Christoffel equation. We found that the obtained C_ijs were in good agreement with previously reported C_ijs at ambient condition. Based on the C_ij values in various conditions, experimental pressures were calculated. The EOS of Pt as a primary pressure scale was determined based on the experimental pressures. We report K’ = 5.17 with fixed K_T = 274.1 GPa and V₀ = 60.360 ų for Vinet EOS. Our scale is in good agreement with several previously published scales based on shock experiments and XRD.     

A Study of Near- and Super-Critical Fluids Using Diamond Anvil Cell and in-Situ FT-IR Spectroscopy

The phase relation and solution structure of water and NaCl aqueous solution have been observed and examined by using the hydrothermal diamond anvil cell (HDAC) at elevated temperatures and pressures and the in situ FT-IR spectroscopy. The temperature of observations ranges from 25 to 850° C and the pressure up to 10 or 30 kb. At first, we observed the phase transition process from halite+liquid+vapour (H+L+V) to L+H, then to L (or supercritical fluid, SCF), and another path: H+L+V? L+V? L (or SCF) in heating process. By means of the visual microscope, the authors found that in the L+V immiscibility field L+V exhibits an ordered structure, i.e. a large visual cluster of solvent around ions. The liquid phase is manifested by vapour bubbles. When phase transitions are observed, the authors examined their infrared spectra by using the FT-IR microscopy simultaneously. In the case of the phase transition from liquid (L) to liquid + vapor (L+V) immisciblity field of NaCl solutions, a sudden change (strong frequency shift) of infrared spectra of the aqueous solution is observed near the critical temperature of water as the temperature is raised from 25 to 650° C. The frequency of the maximum intensity of OH symmetric and asymmetric vibration varies with respect to temperature. The sharp peak of the OH stretching vibration of the maximum intensity appears in an interval from 300 to 400° C. It is indicated that the hydrogen bonding network is weakened and broken at last near the critical point of water, which causes the aqueous solution to become more associated. Besides, a pressure indicator (a mineral or compound) was introduced to the HDAC.     

In situ X-ray observations of phase transitions in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel to 40 GPa using multianvil apparatus with sintered diamond anvils

 Phase transitions in MgAl₂O₄ spinel have been studied at pressures 22–38 GPa, and at temperatures up to 1600 °C, using a combination of synchrotron radiation and a multianvil apparatus with sintered diamond anvils. Spinel dissociated into a mixture of MgO plus Al₂O₃ at pressures to 25 GPa, while it transformed to the CaFe₂O₄ (calcium ferrite) structure at higher pressures via the metastably formed oxide mixture upon increasing temperature. Neither the e-phase nor the CaTi₂O₄-type MgAl₂O₄, which were reported in earlier studies using the diamond-anvil cell, were observed in the present pressure and temperature range. The zero-pressure bulk modulus of the calcium-ferrite-type MgAl₂O₄ was calculated as K=213 (3) GPa, which is significantly lower than that reported by Yutani et al. (1997), but is consistent with a more recent result by Funamori et al. (1998) and that estimated by an ab initio calculation by Catti (2001). Received: 2 April 2002 / Accepted: 29 July 2002 Acknowledgements The authors thank Y. Higo, Y. Sueda, T.␣Ueda, Y. Tanimoto, A. Fukuyama, K. Ochi, F. Kurio and T. Kawahara for help in the in situ X-ray observations at SPring-8 (No: 2000A0061-CD-np and 2000B0093-ND-np). We also thank W.␣Utsumi, J. Ando and O. Shimomura for advice and encouragement during this study, and N. Funamori and an anonymous reviwer for comments on the article. The present study is partly supported by the grant-in-aid for Scientific Research (A) of the Ministry of Education, Science, Sport and Culture of the Japanese government (no: 11694088).