The structures of albite and jadeite composition glasses quenched from high pressure

The structures of jadeite and albite composition glasses quenched from 10 and 15 kbar, respectively, have been studied using radial distribution analysis. It is found that aluminum does not undergo a coordination increase at these pressures, in agreement with recent Raman and NMR studies of these glass compositions. Radial distribution functions (RDF's) indicate that the structural response of albite and Jadeite composition melts to pressure up to 10–15 kbar has to do primarily with a distortion of the tetrahedral sites, a slight collapse of the tetrahedral rings forming the framework, and a small loss of short range order resulting in a more densely packed framework structure. The RDF's do not provide any clues concerning T-O-T angular changes at these pressures. It is suggested that the observed structural changes should be closely related to those that take place in melts of rhyolitic composition. Such changes in rhyolitic melts would result in a density increase and viscosity decrease with increasing pressure similar to that observed for melts of albite and jadeite composition.     

Raman spectra of silicate garnets

The single-crystal polarized Raman spectra of four natural silicate garnets with compositions close to end-members almandine, grossular, andradite, and uvarovite, and two synthetic end-members spessartine and pyrope, were measured, along with the powder spectra of synthetic pyrope-grossular and almandine-spessartine solid solutions. Mode assignments were made based on a comparison of the different end-member garnet spectra and, in the case of pyrope, based on measurements made on additional crystals synthesized with ²⁶Mg. A general order of mode frequencies, i.e. R(SiO₄)>T(metal cation)>T(SiO₄), is observed, which should also hold for most orthosilicates. The main factors controlling the changes in mode frequencies as a function of composition are intracrystalline pressure (i.e. oxygen-oxygen repulsion) for the internal SiO₄-vibrational modes and kinematic coupling of vibrations for the external modes. Low frequency vibrations of the X-site cations reflect their weak bonding and dynamic disorder in the large dodecahedral site, especially in the case of pyrope. Two mode behavior is observed for X-site cation vibrations along the pyrope-grossular binary, but not along the almandine-spessartine join. Received: 3 December 1996 / Revised, accepted: 13 April 1997     

Diffusion of Na,K, Rb and Cs in glasses of albite and orthoclase composition

The measurement of diffusion coefficients for Na, K, Rb and Cs has been realized by the technique of active salt deposits on glasses of albite and orthoclase composition, at normal pressure and in the temperature range 300–1000°C. The values of D are between 10^?6 and 10^?12 cm² s^?1 and, for every type of run, they vary with temperature according to Arrhenius laws, with activation energies ranging from 13 to 68 kcal mole^?1. These important variations are related to the size of the diffusing element (at 700°C in albite glass D_Na/D_K/D_RbD_Cs ～- 10⁷/10⁵/10³/1) and to the size of the major alkali element (for rubidium at 800°C D_or·gl/D_ab·gl ～- 20). By comparison with available data on diffusion in feldspars, we emphasize the influence of the defect density on the diffusion process.     

Raman spectra of gypsum under pressure

Raman sprectra of a gypsum crystal were made at pressures between 0.001 and 7 kbar using He gas as the pressure medium. \(\frac{{{\text{d}}v}}{{dP}}\) values for bands in the range 3,600–100 cm^?1 were obtained. Comparison of results with \(\frac{{{\text{d}}v}}{{{\text{d}}T}}\) from the literature for temperatures of 77 and 300° K. shows that the internal modes of the SO₄ units are more sensitive to pressure than to temperature. The effect is small. Coupled H₂O-SO₄ translational modes are greatly affected by both pressure and temperature while coupled Ca-SO₄ mode are less so. It was found that stretching vibrations of water molecules were affected differently under pressure. The band at 3,500 cm^?1 is more greatly displaced by pressure \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} = {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) than the band at 3,400 cm^?1 \(\left( {\frac{{{\text{d}}v}}{{{\text{d}}P}} \simeq {\text{2}}{\text{.11cm}}^{{\text{ - 1}}} /{\text{kbar}}} \right)\) . Assuming two different hydrogen bond intensities for the water molecules, one can attribute this difference in behavior of stretching modes to and increase in hydrogen bonding of one of the hydrogens which is exterior to the double H₂O planes in the gypsum structure. The great variety of pressure derivatives for the different types of vibrational modes observed indicates that each molecular unit readjusts internally to pressure induced volume changes and the some of the chemical bonds between the units are significantly affected.     

Raman spectra of analcime under pressure

Raman spectra of natural analcime have been recorded at atmospheric pressure and up to 9.4 kbar. The basic Si, Al-O network vibrations are little affected by pressure even though significant volume changes and a minor phase transition take place. However, the 3,557 cm^?1 OH-stretch mode is modified in that band splitting takes place indicating at least two O-OH hydrogen bond distances. Thus there are at least three sites of hydrogen bonding in analcime. The bonded water (H₂O) in analcime appears to remain in the mineral at high pressure. The bulk volume change, determined previously by cell dimension measurements, can be traced to reduction of the size of the “voids” in the structure. This is deduced from the fact that Si-Al-O vibrations are little affected by pressure but O-H vibrations of water molecules found in the voids are strongly pressure-dependent.     

A Raman spectroscopic study of H/D isotopically substituted hydrous aluminosilicate glasses

We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi₃O₈-SiO₂ join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm^–1, whose intensity grows with increasing water content, is extremely small: v _h /v _d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm^–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm^–1 in near-infrared spectra.     

Polarized Raman spectra of beryl and bazzite

The polarized Raman spectra of four different beryl crystals were studied at room temperature in the range from 30 to 4000 cm^-1. The spectra show significant differences between the samples studied, and corrections are proposed for the reference Raman spectra of beryl previously reported by Adams and Gardner (1974). Type II water is observed in two crystals; the corresponding symmetric Raman stretching band at 3595 cm^-1 is extremely strong for an impurity (about 20% of the strongest beryl lattice mode). Another, sharper, band of similar intensity at 3605 cm^-1 could possibly originate from a hydroxyl stretching mode. Additional weaker bands are observed around 1600 cm^-1 and 3600–3750 cm^-1. The first polarized Raman spectra of bazzite are presented and discussed.     

Vibrational spectra of olivine composition glasses: The Mg-Mn join

The vibrational frequencies of a series of splatquenched, olivine glasses spanning the compositional range from Mg₂SiO₄ to Mn₂SiO₄ have been determined using both infrared and Raman spectroscopies. The spectra of all glasses show evidence of tetrahedral coordination of silicon (possibly with some slight distortions), and largely octahedral coordination of magnesium. Spectra of Mn-rich glasses indicate that there is some manganese in 4 or 5-fold coordination. The frequencies observed for the fundamental vibrations of the silica tetrahedra are similar to those previously observed for SiO₄ groups in both crystalline and glassy orthosilicates. Additionally, there is evidence for a small amount of silicate polymerization in all glasses characterized: vibrations attributable to Si₂O₇ groups are visible in both infrared and Raman spectra.     

Transport properties of high albite crystals,near-endmember feldspar and pyroxene glasses,and their melts to high temperature

Thermal diffusivity (D) was measured using laser-flash analysis (LFA) from oriented single-crystal albite and glasses near LiAlSi₃O₈, NaAlSi₃O₈, CaAl₂Si₂O₈, LiAlSi₂O₆ and CaMgSi₂O₆ compositions. Viscosity measurements of the supercooled liquids, over 2.6 × 10⁸ to 8.9 × 10¹² Pa s, confirm strongly non-Arrhenian behavior for CaAl₂Si₂O₈, and CaMgSi₂O₆, and near-Arrhenian behavior for the others. As T increases, D _glass decreases, approaching a constant near 1,000 K. Upon crossing the glass transition, D decreases rapidly. For feldspars, D for the melt is ~15% below D of the bulk crystal, whereas for pyroxenes, this difference is ~40%. Thermal conductivity (k _lat = ρC _P D) of crystals decreases with increasing T, but k _lat of glasses increases with T because heat capacity (C _P ) increases with T more strongly than density (ρ) and D decrease. For feldspars, k _lat for the melt is ~10% below that of the bulk crystal or glass, whereas this decrease for pyroxene is ~50%. Therefore, melting substantially impedes heat transport, providing positive thermal feedback that could promote further melting.     

鄂尔多斯盆地下白垩统含水层储水岩石特征与介质结构研究

本文采用沉积学与水文地质学交叉研究的思路,对鄂尔多斯盆地下白垩统含水层储水岩石特征与含水介质结构进行了研究。下白垩统是由宜君-洛河、华池-环河、罗汉洞-泾川三套含水岩组组成的一个厚达1300m、具多层结构的巨型碎屑岩地下水系统,发育以长石砂岩、长石石英砂岩为主的多类型储水砂岩,其沉积形成于以河流、沙漠为主的多种陆相沉积环境。由于受沉积、成岩及后期剥蚀等作用的控制,各含水岩组储水岩石的类型、厚度及分布,以及储水空间的类型和发育程度、储水孔隙介质结构均有明显变化;在与其它水文地质条件的共同影响下,下白垩统地下水赋存和富集条件总体呈现"盆地北好南差、北部上好下差、南部下好上差"的宏观分布规律。     

和田玉、玛纳斯碧玉和岫岩老玉的拉曼光谱研究

拉曼光谱测定的28件闪石岩类玉石样品中,除玛纳斯碧玉是阳起石外,其他均为透闪石.其拉曼光谱图基本一致,但因受其含FeO量多少的控制,拉曼光谱图也存在一些差别.     

玻璃和熔体包裹体中水含量的拉曼光谱定量测定方面的进展评述

This paper is focused on the progress in the determination of water in glasses and melt inclusions with Raman spectroscopy. Using the presented ＂Comparator Technique＂ the water content of a sample is determined by siruple comparison with a known standard. A calibration curve is not necessary. Furthermore, with this technique the water concentration in silicate melt inclusions can be determined without exposing the inclusions for measurements. This is very important for extremely water-rich melt inclusions, which would loose H2O on exposure.     

实验研究不同盐离子对水分子拉曼效应的影响

对流体包裹体中常见的几种盐水溶液进行了拉曼光谱分析.采用了频移参数描述水分子拉曼峰的形变强度,并讨论了频移参数与盐度之间的关系.实验分析结果表明,盐度越大,频移参数越大,水分子拉曼峰形变越大.对频移参数曲线斜率分析显示,盐类对水分子拉曼峰偏移程度影响的强弱顺序为NaCl＞Na2SO4＞NaHCO3＞Na2CO3.讨论了不同阳离子和阴离子对水伸缩振动拉曼峰的影响,结果表明,高价阳离子的影响明显高于低价阳离子;而阴离子对水拉曼峰影响的强弱顺序初步确定为Cl-≈SO2-4-＞HCO-3＞CO2-3≈NO-3.     

A Raman spectroscopic study of glasses along the joins silica-calcium aluminate,silica-sodium aluminate,and silica-potassium aluminate

Aluminosilicate glasses with compositions along the joins silica-calcium aluminate, silica sodium aluminate and silica-potassium aluminate have been prepared by conventional and solar melting techniques and studied by Raman spectroscopy. The Raman spectra of crystalline calcium aluminate, anorthite and silica polymorphs are discussed in relation to their crystal structures, and compared with the spectra of the corresponding glasses. The glass and crystal spectra are generally comparable, suggesting similar vibrational structures. These crystals have structures based on tetrahedral aluminosilicate frameworks, and a similar molecular structure is suggested for the glasses, although it is noted that the Raman spectra do not directly characterize the aluminate polyhedra. Within the three glass series, our interpretation of the unresolved high-frequency bands shows the appearance of discrete bands near 1120, 1000, 930 and 890 cm^?1 as the silica content is decreased. This is compared with the behaviour of high-frequency bands in simple silicate systems, and used to suggest that the four bands in the aluminosilicate systems are due to stretching vibrations of silicate tetrahedra bound to one, two, three and four aluminium atoms. The spectra of calcium, sodium, potassium and lithium aluminosilicate glasses with similar silica contents are compared, and interpreted by the above model. This is used to construct a simple model for the effect of metal cation on aluminosilicate molecular groups in the glass structure, consistent with the results of calorimetric studies on similar systems.     

The Raman spectra of several orthorhombic calcium oxide perovskites

We have obtained Raman spectra for a number of orthorhombic perovskites CaBO₃, where B=Ti, Ge, Zr or Sn. The room temperature Raman spectrum of CaTiO₃ was compared with cubic SrTiO₃ to assign first- and second-order features. Partially polarized micro-Raman spectra were obtained for CaTiO₃ perovskite. The CaBO₃ perovskites showed a sequence of increasing complexity in their Raman spectra with increasing degree of orthorhombic distortion from the ideal cubic structure. The spectral changes cannot easily be correlated with changes in chemistry or structure of the perovskite. High temperature micro-Raman spectra for CaGeO₃ perovskite were obtained by laser-heating a 15 μm sample. None of the low frequency Raman modes were soft, but showed only normal anharmonicity up to approximately 700 K.     

Raman spectroscopy of ferritungstite: Experimental and model spectra

Raman spectra of ferritungstite are interpreted on the basis of model calculations. The presence of two broad vibrational bands in the spectral range 600–1000 cm^?1 is explained through the combination of two factors. Mainly, two principle bands in the spectral ranges 600–750 and 850–1000 cm^?1 are characteristic of the pyrochlore-type structure attained by ferritungstite and correspond to symmetric and asymmetric stretching of the W-O bonds, respectively. Also, broadening of the Raman lines results from structural disorder caused by the presence of iron atoms.     

A composition-independent quantitative determination of the water content in silicate glasses and silicate melt inclusions by confocal Raman spectroscopy

A new approach was developed to measure the water content of silicate glasses using Raman spectroscopy, which is independent of the glass matrix composition and structure. Contrary to previous studies, the compositional range of our studied silicate glasses was not restricted to rhyolites, but included andesitic, basaltic and phonolitic glasses. We used 21 glasses with known water contents for calibration. To reduce the uncertainties caused by the baseline removal and correct for the influence of the glass composition on the spectra, we developed the following strategy: (1) application of a frequency-dependent intensity correction of the Raman spectra; (2) normalization of the water peak using the broad T–O and T–O–T vibration band at 850–1250 cm⁻¹ wavenumbers (instead of the low wavenumber T–O–T broad band, which appeared to be highly sensitive to the FeO content and the degree of polymerization of the melt); (3) normalization of the integrated Si-O band area by the total number of tetrahedral cations and the position of the band maximum. The calibration line shows a ±0.4 wt% uncertainty at one relative standard deviation in the range of 0.8–9.5 wt% water and a wide range of natural melt compositions. This method provides a simple, quick, broadly available and cost-effective way for a quantitative determination of the water content of silicate glasses. Application to silicate melt inclusions yielded data in good agreement with SIMS data.     

A note on the Goodman Jack

SummaryA Note on the Goodman Jack Reconnaissance experiments, performed to evaluate the practical utility of the hard-rock variety of the Goodman Jack, reveal that the Hustrulid-T^* correction adequately reconciles the discrepancy between the measured and true deformation modulus of the rock mass in the range of 30 to 50 gigapascals.With 3 Figures     

A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Temperature dependence of Raman spectra of the quartz- and rutile-types of GeO2

The temperature dependence (at ambient pressure) of the Raman spectra of both the quartz- and rutile-types of GeO₂ has been studied from 109 to 874?K. All spectra were corrected for the effects of temperature and are presented in their reduced form to allow a direct comparison of intensities at all temperatures. In the quartz-type GeO₂, the Raman bands above 400?cm^?1 exhibited relatively larger temperature dependences and at least four of the bands in this region vary nonlinearly with increasing temperature. Deconvolution of the most intense Raman band at 700?cm^?1 in the rutile-type GeO₂ revealed the presence of a previously unreported band at 684?cm^?1 at 298?K which may arise from splitting of the A_1g mode. A nonlinear temperature dependence was observed for all the Raman bands above 600?cm^?1 in the rutile-type GeO₂ with the new band at 684?cm^?1 exhibiting the largest curvature. In common with previous studies of rutile-type oxides, the B_1g mode at 171?cm^?1 showed anomalous behaviour by increasing linearly in frequency with increasing temperature. In a separate experiment, the oxidation of metallic germanium in air demonstrated that the quartz-type GeO₂ is the preferred form of germanium oxide at temperatures above 745?K at atmospheric pressure. Thermodynamic calculations predict that the rutile-form of GeO₂ should be the stable species under these conditions. This suggests that atmospheric gases may have a marked effect on the kinetics and stability of the quartz and rutile forms of GeO₂.