用红外吸收光谱法研究海泡石的热相变

本文采用红外光谱分析方法，对产于湖北广济的纤维状海泡石的热相变过程进行了分析。     

原位低温拉曼光谱技术在人工合成CaCl2-H2O和MgCl2-H2O体系流体包裹体分析中的应用Ⅱ:低温下流体包裹体相变行为的研究

本文利用低温原位拉曼技术,对CaCl2-H2O体系和MgCl2-H20体系人工合成流体包裹体进行了研究.结果表明:对于盐浓度不同的溶液而言,可采用不同的冷冻方式有效采集低温拉曼光谱;通过系统采集不同温度下的拉曼光谱,可以直接准确地测定包裹体中流体的成分和低温相变过程.人工合成包裹体原位低温拉曼光谱的研究,为将该技术应用于天然包裹体分研究奠定了理论基础,可以预见,该技术必将在流体包裹体研究领域发挥其它方法不可替代的重要作用.     

原位低温拉曼光谱技术在人工合成CaCl2-H2O和MgCl2-H2O体系流体包裹体分析中的应用II：低温下流体包裹体相变行为的研究

本文利用低温原位拉曼技术,对CaCl2-H2O体系和MgCl2-H2O体系人工合成流体包裹体进行了研究。结果表明：对于盐浓度不同的溶液而言,可采用不同的冷冻方式有效采集低温拉曼光谱;通过系统采集不同温度下的拉曼光谱,可以直接准确地测定包裹体中流体的成分和低温相变过程。人工合成包裹体原位低温拉曼光谱的研究,为将该技术应用于天然包裹体分研究奠定了理论基础,可以预见,该技术必将在流体包裹体研究领域发挥其它方法不可替代的重要作用。     

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.     

石英-α型SiO_2高压相变的分子动力学研究

采用在经典离子晶体作用势中附加Morse势 ,并进行必要的量子化修正 ,对石英 α型SiO2 结构随压力变化特性进行分子动力学计算模拟 ,获得了压力高于 2 4 .6GPa ,从晶相向非晶相相变模拟结果 ,并利用其离子间相互作用势、摩尔体积变化、键角等重要信息对模拟结果作了深入的探讨 ,获得了与实验结果较一致的模拟结果。     

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.     

高压相变晶体化学:Ⅰ.高压下SiO_2物相氧硅离子的半径变化和迁移行为

高压下随着压力增加,氧化物及硅酸盐矿物中的阳离子会发生从配位数低的多面体向配位数高的多面体迁移的现象,这种迁移是由于阴阳离子半径的比值发生改变引起的。对SiO2在高压下形成的各种多形的氧和硅的离子半径进行计算,发现氧离子半径是随压力增加及相变的发生而逐渐缩小,但硅离子半径随压力增加及相变的发生而有明显的增大。这种现象可能是在高压下离子化合物逐渐向金属相化合物转变引起的。     

水钠锰矿吸附Pb2+亚结构变化的红外光谱研究

利用红外光谱表征了吸附Pb2+前后的不同锰氧化度的水钠锰矿,结合二次求导退卷积方法确定实际的红外吸收带中心,分析了水钠锰矿红外吸收带的归属.结果表明,供试样品的899～920 cm-1红外吸收带源于八面体空穴处OH的弯曲振动,随着水钠锰矿锰氧化度的降低,空穴处与OH配位的Mn4+被Mn3+替代的数量增多,OH弯曲振动频...     

上地幔超高压流体的金刚石压砧实验研究

地球深部流体主要是NaCl-H2O溶液,越到地球深部,它赋存的温度、压力越高,性质状态也不断变化,反之,亦然。当NaCl-H2O流体进入和脱离(上升过程)超临界状态时,其性质会发生截然不同的变化,影响着各种地质过程。使用金刚石压砧在高温高压下原位观测流体的实验,用谱学方法,结合同步辐射光源技术,成为定量化研究地球深部高温超高压流体的有效方法。作者使用同步辐射光源的红外谱研究了10GPa下的NaCl-H2O溶液;在地球化学动力学实验室研究了3GPa,650℃下的NaCl-H2O溶液红外谱,此测量方法可以提供温度压力和体积等数据,能研究其状态。NaCl-H2O溶液红外谱表明水分子主要振动谱受压力和温度影响是不同的。压力增加促使水分子主要振动谱向低波数变化。但是温度增加的效应相反。常温高压下水被压缩,结晶向紧密堆积变化。高温高压下的水有气、液、固和超临界流体各相。水分子间的氢键在近临界态开始减弱,氢键网络被破坏。     

低温常压条件下NaCl-H_2O体系对铜活化迁移的影响因素Ⅱ:pH值和盐度

文章采用动态模拟实验研究了卤水NaCl-H2O体系不同盐度、酸碱度对砂岩中铜元素的活化迁移作用。结果表明,在常压室温环境下,卤水盐度越高,越有利于含铜砂岩中铜的活化迁移,不同盐度卤水对铜的活化强度表现为w(NaCl)为25%的溶液w(NaCl)为20%的溶液w(NaCl)为10%的溶液w(NaCl)为5%的溶液。酸碱度条件模拟实验,揭示了强酸(pH=0.71)或者强碱(pH=10.28)环境有利于铜的活化迁移,尤其是在强酸(pH=0.71)条件下,可极大增强铜的溶解性,这对于解释蒸发岩盆地含铜卤水的成矿过程具有重要的理论和实际意义。     

Phase relations on the diopside-jadeite-hedenbergite join up to 24 GPa and stability of Na-bearing majoritic garnet

Phase relations on the diopside (Di)-hedenbergite (Hd)-jadeite (Jd) system modeling mineral associations of natural eclogites were studied for the compositions (mol %) Di₇₀Jd₃₀, Di₅₀Jd₅₀, Di₃₀Jd₇₀, Di₂₀Hd₈₀, and Di₄₀Hd₁₀Jd₅₀ using a toroidal anvil-with-hole (7 GPa) and a Kawai-type 6-8 multianvil apparatus (12-24 GPa). We established that Di, Hd, and Jd form complete series of solid solutions at 7 GPa, and melting temperatures of pure Di (1980 °C) and Jd (1870 °C) for that pressure were estimated experimentally. The melting temperature for the Di₅₀Jd₅₀ composition at 15.5 GPa is 2270 °C. The appearance of garnet is clearly dependent on initial clinopyroxene composition: at 1600 °C the first garnet crystals are observed at 13.5 GPa in the jadeite-rich part of the system (Di₃₀Jd₇₀), whereas diopside-rich starting material (Di₇₀Jd₃₀) produces garnet only above 17 GPa. The proportion of garnet increases rapidly above 18 GPa as pyroxene dissolves in the garnet structure and pyroxene-free garnetites are produced from diopside-rich starting materials. In all experiments, garnet coexists with stishovite (St). At a pressure above 18 GPa, pyroxene is completely replaced by an assemblage of majorite (Maj) + St + CaSiO₃-perovskite (Ca-Pv) in Ca-rich systems, whereas Maj is associated with almost pure Jd up to a pressure of 21.5 GPa. Above ∼22 GPa, Maj, and St are associated with NaAlSiO₄ with calcium ferrite structure (Cf). We established that an Hd component also spreads the range of pyroxene stability up to 20 GPa. In the Di₇₀Jd₃₀ system at 24 GPa an assemblage of Maj + Ca-Pv + MgSiO₃ with ilmenite structure (Mg-Il) was obtained. The experimentally established correlation between Na, Si, and Al contents in Maj and pressure in Grt(Maj)-pyroxene assemblages, may be the basis for a “majorite” geobarometer. The results of our experiments are applicable to the upper mantle and the transition zone of the Earth (400-670 km), and demonstrate a wide range of transformations from eclogite to perovskite-bearing garnetite. In addition, the mineral associations obtained from the experiments allowed us to simulate parageneses of inclusions in diamonds formed under the conditions of the transition zone and the lower mantle.     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

Effect of pressure on the thermal expansion of MgO up to 8.2 GPa

Isobaric volume measurements for MgO were carried out at 2.6, 5.4, and 8.2 GPa in the temperature range 300–1073 K using a DIA-type, large-volume apparatus in conjunction with synchrotron X-ray powder diffraction. Linear fit of the thermal expansion data over the experimental pressure range yields the pressure derivative, (∂α/∂P) _T , of −1.04(8) × 10⁻⁶ GPa⁻¹ K⁻¹ and the mean zero-pressure thermal expansion α_{0, T}  = 4.09(6) × 10⁻⁵ K⁻¹. The α_{0, T} value is in good agreement with results of Suzuki (1975) and Utsumi et al. (1998) over the same temperature range, whereas (∂α/∂P) _T is determined for the first time on MgO by direct measurements. The cross-derivative (∂α²/∂P∂T) cannot be resolved because of large uncertainties associated with the temperature derivative of α at all pressures. The temperature derivative of the bulk modulus, (∂K _T/∂T) _P , of −0.025(3) GPa K⁻¹, obtained from the measured (∂α/∂P) _T value, is in accord with previous findings. Received: 2 April 1999 / Revised, accepted: 22 June 1999     

Infrared spectroscopy of CaGeO3 perovskite to 24 GPa and thermodynamic implications

Far-infrared absorbance spectra were collected from CaGeO₃ with a metastable orthorhombic perovskite structure from 0 to 24.4 GPa. The absorbance data are compatible with a reflectance spectrum which was collected at ambient conditions from a polished, densely compacted polycrystal. The reflectance spectrum shows 18 IR modes from 155 to 786 cm^?1. A detailed model for the density of states constructed from these new data results in accurate calculation of heat capacity and new data on entropy. Peak positions increase linearly with pressure. Mode Grüneisen parameters (ranging from 0.72–1.56) decrease almost linearly with increasing mode frequency which is consistent with deformations of the oxygen sublattice dominating the lattice vibrations. Neither discontinuous changes in the number of modes nor in these frequencies nor in band widths are observed at pressures up to 24.4 GPa. Thus, conversion to the tetragonal phase at ～12 GPa is not indicated.     

Thermal diffusivity of silica glass at pressures up to 9 GPa

The thermal diffusivity of silica glass was measured at pressures up to 9 GPa and temperatures up to 1200 K. The measurements involve adopting the Ångström method to a cylindrical geometry in a uniaxial split-sphere apparatus. This method can be used to determine thermal diffusivity in samples with dominant conductive heat transfer. The thermal diffusivity of silica glass has a negative first pressure derivative but a positive second pressure derivative. Although the elastic moduli have minima near 3 GPa, the thermal diffusivity does not has minimum up to 9 GPa, which cannot be explained by the model of Kittel (1949). The negative pressure derivative of thermal diffusivity is a feature probably unique in silica glass, and its magnitude should decrease with the addition of Na₂O.     

Elastic behavior and pressure-induced structure evolution of topaz up to 45 GPa

The behavior of a natural topaz, Al_2.00Si_1.05O_4.00(OH_0.26F_1.75), has been investigated by means of in situ single-crystal synchrotron X-ray diffraction up to 45 GPa. No phase transition or change in the compressional regime has been observed within the pressure-range investigated. The compressional behavior was described with a third-order Birch–Murnaghan equation of state (III-BM-EoS). The III-BM-EoS parameters, simultaneously refined using the data weighted by the uncertainties in P and V, are as follows: K _V = 158(4) GPa and K _V ′ = 3.3(3). The confidence ellipse at 68.3 % (Δχ² = 2.30, 1σ) was calculated starting from the variance–covariance matrix of K _V and K′ obtained from the III-BM-EoS least-square procedure. The ellipse is elongated with a negative slope, indicating a negative correlation of the parameters K _V and K _V ′, with K _V = 158 ± 6 GPa and K _V ′ = 3.3 ± 4. A linearized III-BM-EoS was used to obtain the axial-EoS parameters (at room-P), yielding: K(a) = 146(5) GPa [β _a = 1/(3K(a)) = 0.00228(6) GPa^?1] and K′(a) = 4.6(3) for the a-axis; K(b) = 220(4) GPa [β _b = 0.00152(4) GPa^?1] and K′(b) = 2.6(3) for the b-axis; K(c) = 132(4) GPa [β _c = 0.00252(7) GPa^?1] and K′(c) = 3.3(3) for the c-axis. The elastic anisotropy of topaz at room-P can be expressed as: K(a):K(b):K(c) = 1.10:1.67:1.00 (β _a:β _b:β _c = 1.50:1.00:1.66). A series of structure refinements have been performed based on the intensity data collected at high pressure, showing that the P-induced structure evolution at the atomic scale is mainly represented by polyhedral compression along with inter-polyhedral tilting. A comparative analysis of the elastic behavior and P/T-stability of topaz polymorphs and “phase egg” (i.e., AlSiO₃OH) is carried out.     

High-pressure behavior of natural single-crystal epidote and clinozoisite up to 40 GPa

The comparative compressibility and high-pressure stability of a natural epidote (0.79 Fe-total per formula unit, Fe_tot pfu) and clinozoisite (0.40 Fe_tot pfu) were investigated by single-crystal X-ray diffraction and Raman spectroscopy. The lattice parameters of both phases exhibit continuous compression behavior up to 30 GPa without evidence of phase transformation. Pressure–volume data for both phases were fitted to a third-order Birch–Murnaghan equation of state with V ₀ = 461.1(1) ų, K ₀ = 115(2) GPa, and \(K_{0}^{'}\) = 3.7(2) for epidote and V ₀ = 457.8(1) ų, K ₀ = 142(3) GPa, and \(K_{0}^{'}\) = 5.2(4) for clinozoisite. In both epidote and clinozoisite, the b-axis is the stiffest direction, and the ratios of axial compressibility are 1.19:1.00:1.15 for epidote and 1.82:1.00:1.19 for clinozoisite. Whereas the compressibility of the a-axis is nearly the same for both phases, the b- and c-axes of the epidote are about 1.5 times more compressible than in clinozoisite, consistent with epidote having a lower bulk modulus. Raman spectra collected up to 40.4 GPa also show no indication of phase transformation and were used to obtain mode Grüneisen parameters (γ _i) for Si–O vibrations, which were found to be 0.5–0.8, typical for hydrous silicate minerals. The average pressure coefficient of Raman frequency shifts for M–O modes in epidote, 2.61(6) cm^?1/GPa, is larger than found for clinozoisite, 2.40(6) cm^?1/GPa, mainly due to the different compressibility of FeO₆ and AlO₆ octahedra in M3 sites. Epidote and clinozoisite contain about 2 wt% H₂O are thus potentially important carriers of water in subducted slabs.     

用红外吸收光谱法研究海泡石的热相变

本文采用红外吸收光谱分析方法，对湖北广济海泡石的热相变过程进行了研究。研究 ３００℃以下，海泡石的结构保持稳定：３００－８００℃，海泡的结构发生畸变，形成海泡石酐相；８００℃以上，海泡石的结构被破坏，形成新的矿物相斜顽辉石和方英石。     

Compressions of synthetic pyrope,spessartine and uvarovite garnets up to 25 GPa

The volumes of the pure synthetic pyrope, spessartine and uvarovite garnets have been determined by powder x-ray diffraction as a function of pressure up to 25 GPa in a diamond anvil cell at room temperature. Experiments in different pressure transmitting media have been systematically carried out to determine the effects of anisotropic stress components, which were found to be substantial and have been taken into account. Assuming that the bulk moduli determined from ultrasonic experiments have the lowest uncertainties, the following values for the pressure derivatives of the bulk modulus of uvarovite, spessartine and pyrope were respectively obtained: 4.7±0.7, 7?7.3±1 and 3.4±1. The value for pyrope can be attributed to the small size of the Mg²⁺ cation in its dodecahedral site.     

天然祖母绿与合成祖母绿的成分及红外吸收光谱研究

祖母绿是一种高档名贵的宝石,其矿物学名称为绿柱石,化学成分为铍铝硅酸盐。鉴别天然祖母绿和人工合成祖母绿,已成为祖母绿宝石鉴定中的一个重要课题。文章采用常规宝石学研究方法、激光剥蚀-电感耦合等离子体质谱法和红外光谱技术对天然祖母绿(包括哥伦比亚祖母绿和巴西祖母绿)、合成祖母绿(包括助熔剂法合成祖母绿和水热法合成祖母绿)样品进行了系统的分析和研究。结果表明,天然祖母绿与合成祖母绿的主要致色微量元素Cr的含量越高,祖母绿的绿色越浓艳;天然祖母绿与合成祖母绿的红外吸收光谱特征具有明显的差异;根据祖母绿中是否含水、水的赋存状态以及氯的吸收峰,可作为准确鉴别天然祖母绿和合成祖母绿的重要依据。等离子体质谱法化学成分分析不能确定祖母绿是天然形成还是人工合成,需在常规宝石学检测的基础上,综合研究祖母绿的红外吸收光谱特征及内含物特征,才能准确地鉴别天然祖母绿、水热法合成祖母绿和助熔剂法合成祖母绿。