Equations of state of CaSiO3 Perovskite: a molecular dynamics study

The molar volumes and bulk moduli of CaSiO₃ perovskite are calculated in the temperature range from 300 to 2,800 K and the pressure range from 0 to 143 GPa using molecular dynamics simulations that employ the breathing shell model for oxygen and the quantum correction in addition to the conventional pairwise interatomic potential models. The performance of five equations of state, i.e., the Keane, the generalized-Rydberg, the Holzapfel, the Stacey–Rydberg, and the third-order Birch–Murnaghan equations of state are examined using these data. The third-order Birch–Murnaghan equation of state is found to have a clear tendency to overestimate the bulk modulus at very high pressures. The Stacey–Rydberg equation of state degrades slightly at very high pressures along the low-temperature isotherms. In comparison, the Keane and the Holzapfel equations of state remain accurate in the whole temperature and pressure range considered in the present study. K ₀′ derived from the Holzapfel equation of state also agrees best with that calculated independently from molecular dynamics simulations. The adiabatic bulk moduli of CaSiO₃ perovskite along lower mantle geotherms are further calculated using the Keane and the Mie-Grüneisen–Debye equations of state. They are found to be constantly higher than those of the PREM by ~5%, and also very similar to those of the MgSiO₃ perovskite. Our results support the view that CaSiO₃ perovskite remains invisible in the Earth’s lower mantle.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

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.     

First-principles simulation of high-pressure polymorphs in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>

We have used density functional theory to investigate the stability of MgAl₂O₄ polymorphs under pressure. Our results can reasonably explain the transition sequence of MgAl₂O₄ polymorphs observed in previous experiments. The spinel phase (stable at ambient conditions) dissociates into periclase and corundum at 14 GPa. With increasing pressure, a phase change from the two oxides to a calcium-ferrite phase occurs, and finally transforms to a calcium-titanate phase at 68 GPa. The calcium-titanate phase is stable up to at least 150 GPa, and we did not observe a stability field for a hexagonal phase or periclase + Rh₂O₃(II)-type Al₂O₃. The bulk moduli of the phases calculated in this study are in good agreement with those measured in high-pressure experiments. Our results differ from those of a previous study using similar methods. We attribute this inconsistency to an incomplete optimization of a cell shape and ionic positions at high pressures in the previous calculations.     

Calorimetric study of perovskite solid solutions in the CaSiO3–CaGeO3 system

 Enthalpies of drop solution (ΔH _drop-sol) of CaGeO₃, Ca(Si_0.1Ge_0.9)O₃, Ca(Si_0.2Ge_0.8)O₃, Ca(Si_0.3Ge_0.7)O₃ perovskite solid solutions and CaSiO₃ wollastonite were measured by high-temperature calorimetry using molten 2PbO · B₂O₃ solvent at 974 K. The obtained values were extrapolated linearly to the CaSiO₃ end member to give ΔH _drop-sol of CaSiO₃ perovskite of 0.2 ± 4.4 kJ mol⁻¹. The difference in ΔH _drop-sol between CaSiO₃, wollastonite, and perovskite gives a transformation enthalpy (wo → pv) of 104.4 ± 4.4 kJ mol⁻¹. The formation enthalpy of CaSiO₃ perovskite was determined as 14.8 ± 4.4 kJ mol⁻¹ from lime + quartz or −22.2 ± 4.5 kJ mol⁻¹ from lime + stishovite. A comparison of lattice energies among A²⁺B⁴⁺O₃ perovskites suggests that amorphization during decompression may be due to the destabilizing effect on CaSiO₃ perovskite from a large nonelectrostatic energy (repulsion energy) at atmospheric pressure. By using the formation enthalpy for CaSiO₃ perovskite, phase boundaries between β-Ca₂SiO₄ + CaSi₂O₅ and CaSiO₃ perovskite were calculated thermodynamically utilizing two different reference points [where ΔG(P,T )=0] as the measured phase boundary. The calculations suggest that the phase equilibrium boundary occurs between 11.5 and 12.5 GPa around 1500 K. Its slope is still not well constrained. Received: 20 September 2000 / Accepted: 17 January 2001     

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

Lattice preferred orientation in CaIrO<Subscript>3</Subscript> perovskite and post-perovskite formed by plastic deformation under pressure

Lattice preferred orientations (LPO) developed in perovskite and post-perovskite structured CaIrO₃ were studied using the radial X-ray diffraction technique combined with a diamond anvil cell. Starting materials of each phase were deformed from 0.1 MPa to 6 GPa at room temperature. Only weak LPO was formed in the perovskite phase, whereas strong LPO was formed in the post-perovskite phase with an alignment of the (010) plane perpendicular to the compression axis. The present result suggests that the (010) is a dominant slip plane in the post-perovskite phase and it is in good agreement with the crystallographic prediction, dislocation observations via transmission electron microscopy, and a recent result of simple shear deformation experiment at 1 GPa–1,173 K. However, the present result contrasts markedly from the results on MgGeO₃ and (Mg,Fe)SiO₃, which suggested that the (100) or (110) is a dominant slip plane with respect to the post-perovskite structure. Therefore it is difficult to discuss the behavior of the post-perovskite phase in the Earth’s deep interior based on existing data of MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃. The possible sources of the differences between MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃ are discussed.     

Low-temperature heat capacities,entropies and high-pressure phase relations of MgSiO<Subscript>3</Subscript> ilmenite and perovskite

Low-temperature isobaric heat capacities (C _p ) of MgSiO₃ ilmenite and perovskite were measured in the temperature range of 1.9–302.4 K with a thermal relaxation method using the Physical Properties Measurement System. The measured C _p of perovskite was higher than that of ilmenite in the whole temperature range studied. From the measured C _p , standard entropies at 298.15 K of MgSiO₃ ilmenite and perovskite were determined to be 53.7 ± 0.4 and 57.9 ± 0.3 J/mol K, respectively. The positive entropy change (4.2 ± 0.5 J/mol K) of the ilmenite–perovskite transition in MgSiO₃ is compatible with structural change across the transition in which coordination of Mg atoms is changed from sixfold to eightfold. Calculation of the ilmenite–perovskite transition boundary using the measured entropies and published enthalpy data gives an equilibrium transition boundary at about 20–23 GPa at 1,000–2,000 K with a Clapeyron slope of −2.4 ± 0.4 MPa/K at 1,600 K. The calculated boundary is almost consistent within the errors with those determined by high-pressure high-temperature in situ X-ray diffraction experiments.     

Plastic deformation of orthoenstatite and the ortho- to high-pressure clinoenstatite transition: a metadynamics simulation study

Atomic-scale mechanisms of plastic deformation in orthoenstatite, MgSiO₃ are studied by computer simulation methods. The combined use of metadynamics and molecular dynamics allows a direct observation of the structural changes during the creation of stacking faults in the (100) plane. A sequence of slip deformations in two different (100) planes at P = 15 GPa and T = 1,000 K reveals a probable transformation mechanism for the ortho- to high-pressure clinopyroxene transition. Each of the observed slips consists of at least four partial deformations crossing high-energy intermediate structures. In agreement with experimental studies, both (100)[010] and (100)[001] slip systems are activated in the deformation process. The observation of a dominant (100)[001] single slip system in pyroxenes may be related to the fact that high-energy intermediate dislocations with (100)[010] component are not stable on geological or experimental timescales.     

DFT study of migration enthalpies in MgSiO<Subscript>3</Subscript> perovskite

The effect of pressure on ionic diffusion in orthorhombic MgSiO₃ perovskite has been investigated using density functional theory. An intensive investigation of possible silicon pathways revealed new positions of the saddle-points and an enthalpy of migration at 26.2 GPa of 4.7 eV that is in fair agreement with the experimental values of about 3.5 eV at 25 GPa. This is much lower than found in previous studies (~9 eV) and removes the need to explain silicon diffusion by a complicated process involving coupled oxygen vacancies, as has been previously proposed. Our migration enthalpies for oxygen and magnesium are in excellent agreement with experiments. We find that oxygen diffusion occurs via a chain of several inequivalent jumps along the octahedron edges, and that magnesium occurs via two inequivalent [110] jumps and one [001] jump. We also present activation volumes for all three species at 25 and 135 GPa.     

The stability and compressibility of MgAl2O4 high-pressure polymorphs

High-pressure and high-temperature experiments using a laser-heated diamond anvil cell (LHDAC) and synchrotron X-ray diffraction have revealed a phase transition in MgAl₂O₄. CaTi₂O₄-type MgAl₂O₄ was found to be stable at pressures between 45 and at least 117 GPa. The transition pressure of CaTi₂O₄-type phase in MgAl₂O₄ is much lower than that in the natural N-type mid-oceanic ridge basalt composition. The Birch–Murnaghan equation of state for CaTi₂O₄-type MgAl₂O₄ was determined from the experimental unit cell parameters with K ₀=219(±6) GPa, K ₀′=4(constrained value), and V ₀=238.9(±9) ų. The observed compressibility was in agreement with the theoretical compressibility calculated in a previous study. ε-MgAl₂O₄ was observed at pressures between 40 and 45 GPa, which has not been reported in natural rock compositions. The gradient (dP/dT slope) of the transition from the ε-type to CaTi₂O₄-type MgAl₂O₄ had a positive value. These results should resolve the dispute regarding the stable high-pressure phase of MgAl₂O₄, which has been reported in earlier studies using both the multi-anvil press and the diamond anvil cell.     

Twinning induced by the rhombohedral to orthorhombic phase transition in lanthanum gallate (LaGaO3)

Phase-transformation-induced twins in pressureless-sintered lanthanum gallate (LaGaO₃) ceramics have been analysed using the transmission electron microscopy (TEM). Twins are induced by solid state phase transformation upon cooling from the rhombohedral to orthorhombic (o, Pnma) symmetry at ∼145°C. Three types of transformation twins {101} _o , {121} _o , and {123} _o were found in grains containing multiple domains that represent orientation variants. Three orthorhombic orientation variants were distinguished from the transformation domains converged into a triple junction. These twins are the reflection type as confirmed by tilting experiment in the microscope. Although not related by group–subgroup relation, the transformation twins generated by phase transition from rhombohedral to orthorhombic are consistent with those derived from taking cubic aristotype of the lowest common supergroup symmetry as an intermediate metastable structure. The r→ o phase transition of first order in nature may have occurred by a diffusionless, martensitic-type or discontinuous nucleation and growth mechanism.     

Phase boundary between ilmenite and perovskite structures in MnGeO3 determined by in situ X-ray diffraction measurements

In situ X-ray observations of the phase transition from ilmenite to perovskite structure in MnGeO₃ were carried out in a Kawai-type high-pressure apparatus interfaced with synchrotron radiation. The phase boundary between the ilmenite and perovskite structures in the temperature range of 700–1,400°C was determined to be P (GPa) = 16.5(±0.6) − 0.0034(±0.0006)T (°C) based on Anderson’s gold pressure scale. The Clapeyron slope, dP/dT, determined in this study is consistent with that for the transition boundary between the ilmenite and the perovskite structure in MgSiO₃.     

Interpretation of carbon dioxide diffusion behavior in coals

Storage of carbon dioxide in geological formations is for many countries one of the options to reduce greenhouse gas emissions and thus to satisfy the Kyoto agreements. The CO₂ storage in unminable coal seams has the advantage that it stores CO₂ emissions from industrial processes and can be used to enhance coalbed methane recovery (CO₂-ECBM). For this purpose, the storage capacity of coal is an important reservoir parameter. While the amount of CO₂ sorption data on various natural coals has increased in recent years, only few measurements have been performed to estimate the rate of CO₂ sorption under reservoir conditions. An understanding of gas transport is crucial for processes associated with CO₂ injection, storage and enhanced coalbed methane (ECBM) production.A volumetric experimental set-up has been used to determine the rate of sorption of carbon dioxide in coal particles at various pressures and various grain size fractions. The pressure history during each pressure step was measured. The measurements are interpreted in terms of temperature relaxation and transport/sorption processes within the coal particles. The characteristic times of sorption increase with increasing pressure. No clear dependence of the characteristic time with respect to the particle size was found. At low pressures (below 1 MPa) fast gas diffusion is the prevailing mechanism for sorption, whereas at higher pressures, the slow diffusion process controls the gas uptake by the coal.     

A computer simulation study of OH defects in Mg2SiO4 and Mg2GeO4 spinels

Classical atomistic simulation techniques have been used to investigate the energies of hydrogen defects in Mg₂SiO₄ and Mg₂GeO₄ spinels. Ringwoodite (γ-Mg₂SiO₄) is considered to be the most abundant mineral in the lower part of the transition zone and can incorporate large amounts of water in the form of hydroxyls, whereas the germanate spinel (γ-Mg₂GeO₄) corresponds to a low-pressure structural analogue for ringwoodite. The calculated defect energies indicate that the most favourable mechanisms for hydrogen incorporation are coupled either with the reduction of ferric iron or with the creation of tetrahedral vacancies. Hydrogen will go preferentially into tetrahedral vacancies, eventually leading to the formation of the hydrogarnet defect, before associating with other negatively charged point defects. The presence of isolated hydroxyls is not expected. The same trend is observed for germanate, and thus γ-Mg₂GeO₄ could be used as a low-pressure analogue for ringwoodite in studies of water-related defects and their effect on physical properties.     

Decomposition of kyanite and solubility of Al2O3 in stishovite at high pressure and high temperature conditions

In order to constrain the high-pressure behavior of kyanite, multi-anvil experiments have been carried out from 15 to 25 GPa, and 1,350 to 2,500°C. Both forward and reversal approaches to phase equilibria were adopted in these experiments. We find that kyanite breaks down to stishovite + corundum at pressures above ∼15 GPa, and stishovite + corundum should be the stable phase assemblage at the pressure–temperature conditions of the transition zone and the uppermost part of the lower mantle of the Earth, in agreement with previous multi-anvil experimental studies and ab initio calculation results, but in disagreement with some of the diamond-anvil cell experimental studies in the literature. The Al₂O₃ solubility in nominally dry stishovite has been tightly bracketed by forward and reversal experiments; it is slightly but consistently reduced by pressure increase. Its response to temperature increase, however, is more complicated: increases at low temperatures, maximizes at around 2,000°C, and perhaps decreases at higher temperatures. Consequently, the Al₂O₃ solubility in dry stishovite at conditions of high temperature–high pressure is very limited.     

Ab initio calculations on the O<Subscript>2</Subscript><Superscript>3−</Superscript>-Y<Superscript>3+</Superscript> center in CaF<Subscript>2</Subscript> and SrF<Subscript>2</Subscript>: its electronic structure and hyperfine constants

The O₂ ^3?-Y³⁺ center in fluorite-type structures (CaF₂ and SrF₂) has been investigated at the density functional theory (DFT) level using the CRYSTAL06 code. Our calculations were performed by means of the hybrid B3PW method in which the Hartree–Fock exchange is mixed with the DFT exchange functional, using Becke’s three parameter method, combined with the non-local correlation functionals by Perdew and Wang. Our calculations confirm the stability and the molecular character of the O₂ ^3?-Y³⁺ center. The unpaired electron is shown to be almost exclusively localized on and equally distributed between the two oxygen atoms that are separated by a bond distance of 2.47 Å in CaF₂ and 2.57 Å in SrF₂. The calculated ¹⁷O and ¹⁹F hyperfine constants for of the O₂ ^3?-Y³⁺ center are in good agreement with their corresponding experimental values reported by previous electron paramagnetic resonance and electron nuclear double resonance studies, while discrepancies are notable for the ⁸⁹Y hyperfine constants.     

X-ray Raman scattering for structural investigation of silica/silicate minerals

We have performed X-ray Raman scattering (XRS) measurements on the oxygen K and silicon L absorption edges of four silica minerals: α-quartz, α-cristobalite, coesite, and stishovite. We have also calculated the partial electron densities of states (DOSs) and compared these with the XRS spectra. This study demonstrates that the short-range structure around the atom of interest strongly influences the XRS spectral features. Importantly, the oxygen K-edge XRS spectra are found to reflect the p-orbital DOS while the silicon L-edge spectra reflect the s- and d-orbital DOSs, even when a product of a momentum transfer and a mean radius of a electron orbit (1s for oxygen and 2p for silicon), Qr, is close to or larger than unity. Building on this, calculations of the partial DOSs for other silica phases are presented, including ultra-high-pressure phases, which provide a good reference for further XRS study of silica and silicate minerals. XRS measurements should be performed on not only either of oxygen or silicon but also on many kinds of constituent elements to reveal the structural change of glasses/melts of silicates under extreme conditions.     

碱处理对河北围场天然沸石结构和性能的影响及其机理研究

采用NaOH对围场地区天然沸石进行处理,采用X射线衍射仪、红外光谱仪、N2吸附-脱附技术、扫描电子显微镜等对材料进行表征分析,采用水蒸气吸附法评价材料的亲水性,采用Cr3+和Mn2+评价材料的离子交换性能,探讨了碱处理对天然沸石的结构、亲水性和离子交换性能的影响及其机理.实验结果表明,围场地区天然沸石中主要含有斜发沸石...     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.