Ab initio investigation into the elasticity of ultrahigh-pressure phases of SiO2

In this study, we report the elastic properties of three ultrahigh-pressure phases of SiO₂: pyrite, cotunnite and Fe₂P types between 300 and 1,500 GPa calculated by means of the density functional ab initio method. It is generally thought that materials tend to be more compact and isotropic with increasing pressure. These three ultrahigh-pressure phases of silica are mechanically stable in the investigated pressure range according to the Born criteria, while the cotunnite and Fe₂P types are unstable at lower pressure. The elastic azimuthal anisotropy of these ultrahigh-pressure phases of silica shows that all the structures counterintuitively have considerable anisotropies even at multimegabar pressures. Among the three investigated structures, the cotunnite type of SiO₂ is the most elastically anisotropic phase due to a soft compression along the b axis combined with a large distortion of the polyhedrons that make the structure. This might also be related to its thermodynamic unfavorability compared to the Fe₂P type under extreme pressure condition. The bond property analyses clearly show that the Si–O bond remains an ionic-covalent mixed bond even at multimegabar pressures with an invariable ionicity with pressure. This argument can explain the monotonously pressure dependence of the elastic anisotropy in the case of pyrite, while the changes in the velocity distribution patterns out of the thermodynamic instability range largely contribute to those of the cotunnite and Fe₂P types.     

A transferable interatomic potential for crystalline phases in the system MgO—SiO2

A central interatomic potential model is presented for compounds in the binary system MgO-SiO₂. The potential, of a simple form which consists of a Coulombic term, a Born repulsive term, and a Van der Walls term for oxygen-oxygen interactions, is designed to predict the properties of magnesium silicates containing Si in octahedral and tetrahedral coordination. This is achieved by fitting simultaneously to forsterite and MgSiO₃ ilmenite crystal structure data, and fixing the partial ionic charges using elastic data for forsterite. The potential is found to transfer successfully to γ-Mg₂SiO₄ and MgSiO₃ perovskite. The potential results in local structural errors around the bridging oxygen ions in clinoenstatite and β-Mg₂SiO₄. The predicted structure for MgSiO₃ garnet is similar to the experimentally measured structure of the MnSiO₃ analogue. Calculated elastic constants average to K=2.41 Mbar and μ=1.44 Mbar for the bulk and shear moduli of MgSiO₃ perovskite, and K=1.87 Mbar and μ=1.10 Mbar for the bulk and shear moduli of MgSiO₃ garnet.     

基于钻探约束的瞬变电磁解释方法及应用

随着我国城镇建设的飞速发展,城镇建筑用地范围不断扩大,所面临的近地表地质构造越来越复杂,常规钻探法难以满足地基勘查的需要。为此,基于优势互补理念,将瞬变电磁法空间采样率高、地质信息丰富、地质体横向边界刻画准确等优势与钻探垂向测深精度高、分层定位准确等优势相结合,提出基于钻探约束的瞬变电磁法解释新方法,较好地克服了常规瞬变电磁法计算深度精度不足的局限,提高了视电阻率剖面的纵向解释能力。通过浩金元住宅建设区采空区探测的应用试验,圈定了测区中东部存在一个面积约0.01 km²的采空积水区,中部存在一个面积约0.009 75 km²的非采空区,其他部分均为采空区,取得了良好的应用效果。     

Molecular dynamics interpretation of structural changes in quartz

 Constant temperature and constant pressure molecular dynamics (MD) simulations were applied to quartz to calculate the structural details which are indeterminable in usual X-ray structure studies. The dynamics of the structural changes was analyzed by means of time-dependent atomic displacement parameters. The Si-O bonds expand with increasing temperatures through the α- and β-phases, and atoms vibrate around the α₁- (or α₂-) sites at lower temperatures in the α-phase, and over the energy barriers between the α₁- and the α₂-sites at higher temperatures in the α- and the β-phases. The ratios of time lengths spent by atoms in the α₁- and α₂-sites determine the apparent atomic positions as obtained in usual structure studies of α-quartz. More frequent transfer of atoms over the α₁- and the α₂-sites contributes positively to the thermal expansions, whereas larger amplitudes of vibrations, which carry atoms more distantly and more frequently from the β-sites, contribute negatively. The well-known steep thermal expansion in the α-phase is attributed to the additive contribution from the expansions of the Si-O bond lengths, the widening of Si-O-Si angles, and the increase of the atomic transfer-frequency between the α₁- and the α₂-sites. The nearly zero or negative expansion in the β-phase is caused by balancing the negative to the positive effects. The MD crystal transforms to the β-phase via a transitional state, where the α- and β-structures appear alternately with time, or coexist. The slight and continuous expansions observed right after the steep rise(s) of the volume or cell dimensions up to the nearly horizontal curve(s) are attributed to the continuous changes within the transitional state. Received: 17 July 2000 / Accepted: 13 January 2001     

High temperature structural investigation of Na2O·0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 melts and glasses

The structure of glasses and melts of Na₂O· 0.5Fe₂O₃·3SiO₂ and Na₂O·FeO·3SiO₂ compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe³⁺ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe³⁺ is tetrahedrally coordinated in the oxidized glass and part of the Fe²⁺ is tetrahedrally coordinated in the reduced glass.     

三分量定源瞬变电磁解释技术及其在金属矿区的实验

目前的瞬变电磁仪器已经为三分量瞬变电磁解释提供了硬件基础,但瞬变电磁的实用解释技术仍局限于对垂直分量的解释或一些简单近似技术。为充分利用三分量数据,进一步提高定源瞬变电磁方法的分辨率,针对定源瞬变电磁装置给出三分量全域视电阻率定义和三分量联合一维反演的方法。在进行全域视电阻率定义时,利用迭代求取反函数值的方法替代直接求取反函数的过程;引入三分量瞬变电磁数据的权重以构建联合三分量数据的目标函数,利用可行域法实现三分量联合一维瞬变电磁反演;最后将三分量解释算法分别应用在模型计算和金属矿的实际勘查资料上,以检验其有效性。模型试验和实际资料处理结果表明,三分量解释方法能够利用更多的瞬变电磁数据,获得更高分辨率的处理结果,且具有较快的计算速度。     

Solubility of water in the α, β and γ phases of (Mg,Fe)2SiO4

 The solubility of hydroxyl in the α, β and γ phases of (Mg,Fe)₂SiO₄ was investigated by hydrothermally annealing single crystals of San Carlos olivine. Experiments were performed at a temperature of 1000° or 1100 °C under a confining pressure of 2.5 to 19.5 GPa in a multianvil apparatus with the oxygen fugacity buffered by the Ni:NiO solid-state reaction. Hydroxyl solubilities were determined from infrared spectra obtained of polished thin sections in crack-free regions ≤100 μm in diameter. In the α-stability field, hydroxyl solubility increases systematically with increasing confining pressure, reaching a value of ∼20,000 H/10⁶Si (1200 wt ppm H₂O) at the α-β phase boundary near 13 GPa and 1100 °C. In the β field, the hydroxyl content is ∼400,000 H/10⁶Si (24,000 wt ppm H₂O) at 14–15 GPa and 1100 °C. In the γ field, the solubility is ∼450,000 H/10⁶Si (27,000 wt ppm H₂O) at 19.5 GPa and 1100 °C. The observed dependence of hydroxyl solubility with increasing confining pressure in the α phase reflects an increase in water fugacity with increasing pressure moderated by a molar volume term associated with the incorporation of hydroxyl ions into the olivine structure. Combined with published results on the dependence of hydroxyl solubility on water fugacity, the present results for the α phase can be summarized by the relation C _OH = A(T)f nH₂Oexp(−PΔV/RT), where A(T) = 1.1 H/10⁶Si/MPa at 1100 °C, n = 1, and ΔV = 10.6×10^–6 m³/mol. These data demonstrate that the entire present-day water content of the upper mantle could be incorporated in the mineral olivine alone; therefore, a free hydrous fluid phase cannot be stable in those regions of the upper mantle with a normal concentration of hydrogen. Free hydrous fluids are restricted to special tectonic environments, such as the mantle wedge above a subduction zone. Received: 10 February 1995 / Accepted: 23 October 1995     

Modelling of structural and elastic changes of forsterite (Mg2SiO4) under stress

The method of crystal static deformation, including inner strain effects, was applied to calculate the structure configuration and the elastic constants of forsterite under anisotropic and isotropic pressure. A Born type interatomic potential is used, with optimized atomic charges and repulsive radii; SiO₄ tetrahedra are approximated as rigid units. Computations were carried out in the range 1–8 GPa, with steps of 1 GPa, for the three uniaxial stresses τ₁, τ₂, τ₃ and for pressure p. By interpolation of results, interatomic distances and elastic tensor components are shown to depend quadratically on stress. A non-linear behaviour generally appears above 4 GPa; the importance of inner strain and non-linear effects is analyzed. Mg-O bond lengths and O-O edges of coordination polyhedra respond differently to anisotropic and to isotropic stresses, according to the topological features of the structure. Elastic and structural results for hydrostatic pressure are compared to experimental literature data, discussing the range of validity of the rigid body approximation for SiO₄ groups.     

The structural role of Al2O3 and TiO2 in immiscible silicate liquids in the system SiO2-MgO-CaO-FeO-TiO2-Al2O3

The effects of the addition of Al₂O₃ on the large stable two liquid field in the SiO₂-TiO₂-CaO-MgO-FeO system were experimentally determined. The increase of Al₂O₃ content in the starting composition results in the decrease of critical temperature, phase separation and liquidus temperature of the two liquid field until it is rendered completely metastable. The shrinkage of the two liquid field indicates that Al₂O₃ is acting in the role of a network former and homogenizes the structure of the two melts. In this alkali-free system Al⁺³ utilizes the divalent cations, Ca⁺² and Mg⁺², for local charge balance with a preference for Ca⁺² over Mg⁺². Thus, AlO₄ tetrahedra combine with SiO₄ tetrahedra to form an aluminosilicate framework which polymerizes the SiO₂-poor melt and makes it structurally more similar to the SiO₂-rich melt. However, Ca⁺² and Mg⁺² are not as efficient in a charge balancing capacity as the monovalent K⁺ and Na⁺ cations. The lack of alkalis in this system limits the stability of AlO₄ tetrahedra in the highly polymerized SiO₂-rich melt and results in the preference of Al₂O₃ for the SiO₂-poor melt. The partitioning systematics of Ti are virtually identical to those of Al. It is concluded that Ti occurs in tetrahedral coordination as a network forming species in both the high — and low — SiO immiscible melts.     

The two polymorphs of TlPbSbS3 and the structural relations of phases in the system TlSbS2-PbS

Summary The synthetic TlPbSbS₃ represents a rare example of a sulphosalt with statistical distribution of Tl, Pb and Sb in the structure. Within the TlSbS₂-PbS system, TlPbSbS₃ is the end member of the solid solution series with TlSbS₂, but no solubility with PbS is detected. The high temperature-TlPbSbS₃ is orthorhombic and inverts at about 620 K to the low-temperature phase. The low-temperature modification of TlPbSbS₃ was structurally investigated by X-ray powder diffraction and by the Rietveld analysis of the data. The structure is monoclinic, with a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, space group P2₁/c. Like in the high-temperature form, there is a cation disorder over the equivalent positions in the structure. The interatomic distances of (Tl, Ph, Sb) to S are 2.71, 2.72, 2.88, 3.15, 3.29, 3.51 (Å). There is a close similarity between the TlPbSbS₃ polymorphs and the and forms of SnS, as regards the atomic coordinations and the general structure types and the same type of phase transformation is supposed for both cases. The small differences in the structure type and symmetry, between the low temperature forms of SnS and TlPbSbS₃, result probably from stronger metal-metal interactions in the latter. A substitution-derivative relation to SnS type is established owing to the strong structural effect of the lone electron pairs of Tl and Sb. The substitution of Ag for Tl and Bi for Sb in ABCS₃ type compounds diminishes this effect and PbS type structures are produced.

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Die zwei Polymorphen von TlPbSbS₃ und die Strukturellen Beziehungen von Phasen in System TlSbS₂-PbS

Zusammenfassung Die synthetische Phase TlPbSbS₃ ist ein seltenes Beispiel von einem Sulfosalz mit der statistischen Verteilung von TI, Pb und Sb in der Struktur. In der TlSbS2-PbS Phasensystem, ist TlPbSbS₃ das Endmitglied der Mischkristallreihe, die sich im Richtung TlSbS₂ ausstreckt. Weitere Ausdehnung der Mischkristallreihe in der Richtung SbS konnte nicht bewiesen werden. Die Hochtemperatur-TlPbSbS₃ ist rhombisch und wird beim 620 K in die Tieftemperatur Modifikation umgewandelt. Die Tieftemperaturphase ist mit der Röntgenpulverdiffraktion und Rietveld Methode strukturell untersucht worden. Die ist monoklin, mit den Gitterkonstanten: a = 4.1707(4) Å, b = 4.2856(4) Å, c = 12.157(1) Å, = 105.49(1)°, Raumgruppe P2₁/c. Die statistische Verteilung von Kationen ist auch hier vorhanden. Die zwischenatomare Abstande (Tl, Pb, Sb)-S sind: 2.71, 2.72, 2.88, 3.14, 3.28, 3.51 (Å). Es besteht eine enge Verwandschaft zwischen den polymorphen Modifikationen von TlPbSbS₃ und den und Polymorphen von SnS, was die atomare Koordinationen und den generellen Strukturtypus betrifft, wobei ein ähnlicher Mechanismus der Phasenumwandlung für die beiden Fälle vermutet werden könnte. Die Differenzen in der Struktur und Symmetrie zwischen der Tieftemperaturmodifikationen von SnS und TlPbSbS₃ sind wahrscheinlich durch die bedeutende Metall-Metall Wirkungen in der zweiten verursacht. Die Phase TlPbSbS₃ ist ein substitution-derivative von der SnS Struktur, was durch die starke lone-electron-pair Aktivität von Kationen zu erklären ist. Die Ersetzung von Tl durch Ag und Sb durch Bi vermindert diese Aktivität und die entstandenen Strukturen sind in dem Fall dem PbS-Typus verwandt.

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With 3 Figures     

EPR Parameter of Order Degree in Natural Kaolinite and Its Relation to Weathering

Conclusions In studying the degree of order (or disorder) in kaolinite, X-ray diffraction and DTA are commonly used, but spectroscopic method (as EPR, IR)has become a useful and additional tool now. The total iron content and the intensity of Fe³⁺(I) line are not always correlated negatively with order degree in natural kaolinite. But in the present case, they show direct correlations. So it appears that they cannot be used as an ideal parameter for measuring the order degree in kaolinite. The ratio of Fe³⁺(E)line and Fe³⁺(I)line intensities obtained directly from EPR spectrum of Fe³⁺at g_eff=4 appears to be a better EPR parameter for measuring the magnitude of order degree in kaolinite and for determining the intensity of some geological processes (such as weathering, hydrothermal alteration and so on) with aid of kaolinite. However, EPR data can only be used to qualitatively estimate the degree of order in kaolinite and related geological process for the present. There is still much work to be done in order to make EPR a method of quantitative estimation in the field.     

Computer simulations of the structural and physical properties of the olivine and spinel polymorphs of Mg2SiO4

The aim of the work presented is to develop a computer simulation technique which will predict the structure and physical properties of forsterite and ringwoodite, the major mantle-forming polymorphs of Mg₂SiO₄. The technique is based upon energy minimization, in which all structural parameters are varied until the configuration with the lowest energy is achieved. The lattice energy and physical properties (e.g. elasticity and dielectric constants) are calculated from interatomic potentials, which generally include electrostatic and short-range terms. We investigate several types of traditional potential models, and present a new type of model which includes partial ionic charges and a Morse potential to describe the effect of covalency on the Si-O bond. This new form of potential model is highly successful, and not only reproduces the zero-pressure structural, elastic and dielectric properties of forsterite and ringwoodite, but also accurately describes their pressure dependence.     

Stability of dense hydrous magnesium silicate phases in the systems Mg2SiO4-H2O and MgSiO3-H2O at pressures up to 27 GPa

We conducted high-pressure phase equilibrium experiments in the systems MgSiO₃ with 15 wt% H₂O and Mg₂SiO₄ with 5 wt% and 11 wt% H₂O at 20 ∼ 27 GPa. Based on the phase relations in these systems, together with the previous works on the related systems, we have clarified the stability relations of dense hydrous magnesium silicates in the system MgO-SiO₂-H₂O in the pressure range from 10 to 27 GPa. The results show that the stability field of phase G, which is identical to phase D and phase F, expands with increasing water contents. Water stored in serpentine in the descending cold slabs is transported into depths greater than 200 km, where serpentine decomposes to a mixture of phase A, enstatite, and fluid. Reaction sequences of the hydrous phases which appear at higher pressures vary with water content. In the slabs with a water content less than about 2 wt%, phase A carries water to a depth of 450 km. Hydrous wadsleyite, hydrous ringwoodite, and ilmenite are the main water reservoirs in the transition zone from 450 to 660 km. Superhydrous phase B is the water reservoir in the uppermost part of the lower mantle from 670 to 800 km, whereas phase G appears in the lower mantle only at depths greater than 800 km. In cold slabs with local water enrichment greater than 2 wt%, the following hydrous phases appear with increasing depths; phase A to 450 km, phase A and phase G from 450 km to 550 km, brucite, superhydrous phase B, and phase G from 550 km to 800 km, and phase G at depths greater than 800 km. Received: 4 August 1999 / Accepted: 1 March 2000     

Al-Si order and degree of disturbance of perthites from the Upper Amur region

Doklady Earth Sciences -     

盐岩地下储气库泥岩夹层分布与组构特性研究

以江苏金坛地下盐岩储气库为例,在区域地质与场地工程地质条件分析的基础上,通过盐岩及夹层分布与岩性分析、泥岩夹层全岩X光衍射试验、黏土矿物X光衍射试验及定量分析、泥岩夹层的粒度试验、崩解试验及水理试验研究表明,金坛地下储气库岩盐层夹层主要为层间夹层与层内夹层,盐岩层间夹层分布稳定,厚度较大,不溶物含量高;盐岩层内夹层层数多,厚度薄,分布不均,不溶物含量低。盐岩层间泥岩夹层的主要矿物为黏土矿物,黏土矿物的主要存在形式为伊利石/蒙脱石混成矿物;泥岩夹层主要为细粒颗粒;泥岩夹层沿层理面崩解,层状开裂软化,具有微膨胀性。对于储库水溶建腔速度、成腔形状与运营期的腔体蠕变具有重要影响。     

平衡剖面技术在龙门山中段构造解释中的应用

龙门山推覆冲断带地形条件恶劣,构造断裂复杂,阻碍了该区油气资源的勘探进程。为搞清龙门山推覆冲断带下的构造样式,验证其构造解释方案,应用平衡剖面技术,对龙门山中段具典型构造特征的地质、地震综合解释剖面进行平衡恢复。实例分析证明,平衡剖面技术可正确指导龙门山中段构造剧烈变形区的构造解释方案,并可定性、定量分析构造变形期次和变形程度,为下一步油气勘探提供可靠依据。     

Texture and structural interpretation of the alteration of pyroxene to other biopyriboles

In a metamorphosed gabbro from Hokkaido, Japan, augite containing exsolved orthohypersthene and minor pigeonite has been altered to a variety of biopyriboles. High resolution transmission electron microscopy of slightly altered augite shows only narrow (010) lamellae of clinoamphibole which always contain even numbers of double chains. In more highly altered regions, all three pyroxenes are changed to double-, triple- and more highly polymerized multiple-chain biopyriboles, with chlorite d ₀₀₁ 14.5 Å) found only in orthopyroxene. Several (010) lamellae containing only one double chain have been observed, and their textural relationship to the surrounding single-chain host may explain how the rotated domains of biopyribole initially attain their orientation in the host pyroxene.A structural model is proposed for the polymerization of single chains in the tetrahedral layers of pyroxene which involves small movements of oxygens and tetrahedral atoms (Si, Al) with a minimum of bond breaking and re-forming, concommitant with hydroxylization of certain oxygens and the diffusion of Mg, Fe and/or Ca along the rift in the octahedral layer.     

Energy gap and density in SiO2 polymorphs

A relationship between the energy gap (E _G) and density (ρ) for pure SiO₂ polymorphs is derived from atomic weights and first ionization potentials of free silicon and oxygen atoms. Theoretical considerations are based on the Lorentz electron theory of solids. The eigenfrequency v₀ of elementary electron oscillators, in energy units h v₀, is identified with the energy gap of a solid. The numerical relation is expressed as \(E_G = \sqrt {139.24 - 13.8327\rho } \) is in eV. For low-quartz with a density of 2.65 g/cm³ and also for stishovite with a density of 4.28 g/cm³, the energy gap E _G=10.1 eV and 8.9 eV, respectively. From laboratory measurements for low-quartz E _G=10.2 eV. The energy gap-density relation suggests a critical density value of ρ_x ≈ 10.1 g/cm³ for an SiO₂ phase when the energy gap vanishes (E _G=0), which is consistent with estimated densities for a high pressure silica polymorph with the fluorite structure.