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.     

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.     

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.     

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.     

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.     

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.     

CaPtO3 as a novel post-perovskite oxide

Structural, morphological, magnetic, and thermal properties have been investigated for a novel post-perovskite oxide CaPtO₃ synthesized under high pressure. By comparing obtained structural parameters with those for known post-perovskite compounds, we argue that the chemical bond has a strong covalent character. Precise measurements of the Langevin susceptibility χ ₀ = −9.6 × 10⁻⁵ emu/mol and Debye temperature θ ∼ 470 K provide a good opportunity to confirm the reliability of first-principle calculations on predicting physical properties of the Earth’s D” layer.     

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.     

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...     

H2O2在α-Fe2O3表面非均相氧化SO2机理的模拟研究

通过密度泛函理论模拟了H_2O_2和SO_2气体在矿物氧化物(α-Fe_2O_3)表面上的非均相反应,研究了H_2O_2和SO_2在α-Fe_2O_3(001)表面的吸附机制和氧化机制。研究结果表明,SO_2、H_2O_2均在α-Fe_2O_3(001)表面通过Fe原子进行吸附,H_2O_2相比于SO_2优先吸附在α-Fe_2O_3(001)表面,且H_2O_2在表面的赋存形式趋向于两个·OH形式吸附。通过二者共吸附的局域态密度、差分电荷密度、Mulliken电荷布局分析结果发现,SO_2和H_2O_2的共吸附形式是通过H_2O_2产生的·OH吸附在α-Fe_2O_3(001)表面,同时SO_2被H_2O_2产生的·OH氧化[S(SO_2)-电荷布局:0. 79 e→1. 32 e; O(H_2O_2)-电荷布局:-0. 77 e→-1. 11 e]形成·OH+SO_2团簇。模拟结果表明大气微量气体H_2O_2能够在矿物氧化物表面介导SO_2吸附并促进SO_2的转化,为理解H_2O_2在大气中非均相氧化SO_2的反应过程提供了理论依据。     

Temperature dependence of the polarized electronic absorption spectra of olivines. Part II—Cobalt-containing olivines

Polarized electronic absorption spectra of single crystalline Co₂[SiO₄] and (Co_0.64Mg_0.36)₂[SiO₄] (E|| a (|| Z), E || b (|| X), E || c (|| Y)) have been studied in the temperature range 293 T/K 1273. The three polarized spectra show a total of 15 bands. Five bands are caused by spin-allowed transitions in Co²⁺ ions at M1 sites which appear in all polarization directions. Seven polarization-dependent bands can be ascribed to spin-allowed transitions in Co²⁺ ions at M2 sites and three bands may be assigned to spin-forbidden transitions. The assignment of bands due to Co²⁺ ions at M1 and M2 sites has been made on the basis of transition energies and intensity ratios. Further arguments have been derived from the comparison of spectra of crystals with different cobalt content, from the analysis of the polarization dependence of the spectra, and from the evolution of band intensities with temperature.     

四川昭觉地区优质偏硅酸地下水的特征、成因及其开发利用建议

【研究目的】近年来,随着生活水平的不断提高,人们对健康饮水的要求也在不断提高,寻找与开发富含H₂SiO₃等矿物质优质地下水已成为关键。【研究方法】本文以昭觉地区水文地质调查工程、地下水污染调查工程所获取的地下水化学数据为基础,探讨了昭觉地区富H₂SiO₃地下水的分布特点、元素水文地球化学特征、形成条件及成因。【研究结果】结果显示：（1）全县富H₂SiO₃（≥25 mg/L）地下水均属于低矿化度偏碱性水,分布在基底岩石为玄武岩的6个片区,H₂SiO₃含量一般介于25.74~46.04 mg/L,pH含量一般介于7.4~8.58,TDS含量一般介于49.4~333 mg/L;（2）玄武岩地下水存在HCO₃－Ca、HCO₃－Ca·Mg、HCO₃－Ca·Na、HCO₃－Ca·Mg·Na、HCO₃－Na等5种水化学类型,总体以HCO₃－Ca · Mg为主,其次为HCO₃－Ca,再次为HCO₃－Ca · Na,三者分别占总采样点数的50.00%、25.76%、12.12%;（3）全县富H₂SiO₃地下水的形成受水岩相互作用、硅酸盐矿物的分布范围及其可溶性、围岩裂隙发育程度、水源涵养及补给条件等四方面因素影响,其中水岩相互作用占据主导作用;（4）在后续开发利用过程中,需进一步揭示影响地下水中H₂SiO₃分布与迁移的因素。【结论】研究结果可以为昭觉地区矿泉水产业的发展及城乡优质水源地的建设提供依据。创新点：系统总结了昭觉县优质偏硅酸地下水空间分布特征和水化学特征;从形成条件与水岩作用的角度探讨了优质偏硅酸地下水的形成机制。     

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.     

基于ASTER的哈密土墩地区构造及蚀变信息提取与找矿预测

土墩铜镍矿位于东天山黄山—镜儿泉铜镍成矿带, 矿床形成主要受岩浆作用和构造作用控制。为了进一步探测该地区的矿产情况, 采用ASTER热红外波段比值组合模拟的反演算法, 对发射率数据进行SiO₂含量的定量反演, 在反演图上识别出了研究区内明显的石英断裂带。结合ASTER数据可见光—近红外光谱波段中提取出的构造信息, 得出研究区完整的构造解译图。采用主成分分析和阈值分割法对研究区进行了铁染、羟基蚀变信息提取。最后根据区内线性构造、遥感蚀变信息、岩石分布特征、化探异常、已知矿床点分布资料综合分析, 圈定出6个成矿有利区, 为研究区今后的找矿勘查提供依据。      

SO2和NO2在白云母表面的非均相反应研究

白云母是大气中矿物气溶胶的重要组分之一,研究大气中常见气体在其表面的非均相反应,在一定程度上可揭示大气环境中化学反应过程。文章采用自制石英玻璃微型反应器研究了SO₂和NO₂在白云母颗粒物表面的非均相反应,并探讨了相对湿度(RH)及光照对该反应的影响。结果表明,白云母对SO₂和NO₂均有一定的吸附活性,有紫外光和无紫外光条件下,SO₂的反应产物分别以SO^2-₄和SO^2-₃为主,NO₂的产物均以NO^-₃为主;RH或者紫外光照对反应均具有促进作用,两者对硫酸盐和硝酸盐的生成有协同效应;当SO₂和NO₂在白云母表面共存时,既有协同作用又存在竞争反应,SO^2-₄和NO^-₃的生成量分别是SO₂、NO₂单独存在的2.09倍和77%。因此,NO₂能促进硫酸盐的生成,但SO₂对硝酸盐的生成有明显抑制作用。     

Low-temperature heat capacities of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> and spinels of the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution

We present results from low-temperature heat capacity measurements of spinels along the solid solution between MgAl₂O₄ and MgCr₂O₄. The data also include new low-temperature heat capacity measurements for MgAl₂O₄ spinel. Heat capacities were measured between 1.5 and 300 K, and thermochemical functions were derived from the results. No heat capacity anomaly was observed for MgAl₂O₄ spinel; however, we observe a low-temperature heat capacity anomaly for Cr-bearing spinels at temperatures below 15 K. From our data we calculate standard entropies (298.15 K) for Mg(Cr,Al)₂O₄ spinels. We suggest a standard entropy for MgAl₂O₄ of 80.9 ± 0.6 J mol⁻¹ K⁻¹. For the solid solution between MgAl₂O₄ and MgCr₂O₄, we observe a linear increase of the standard entropies from 80.9 J mol⁻¹ K⁻¹ for MgAl₂O₄ to 118.3 J mol⁻¹ K⁻¹ for MgCr₂O₄.     

HONO在γ-Al2O3(110)表面非均相氧化SO2机理的第一性原理研究

为研究亚硝酸(HONO)在γ-Al_2O_3(110)表面非均相氧化SO_2的机理,基于密度泛函理论(density functional theory,DFT)的第一性原理计算了SO_2和HONO在γ-Al_2O_3(110)表面的吸附机制和氧化机制。结果表明,SO_2以分子的形式吸附在完整或缺陷的γ-Al_2O_3(110)表面,而HONO仅在完整表面上以分子的形式存在。表面氧缺陷的存在不仅会增强SO_2和HONO的吸附强度,而且能诱导HONO在含氧缺陷表面的分解(HONO→NO+·OH)。通过局域态密度(partial density of states,PDOS)和Mulliken电荷布局分析表明,HONO的分解遵循Haber-Weiss机制。当SO_2和HONO共同吸附在氧缺陷表面时,HONO分解产生·OH,氧化SO_2形成HOSO_2团簇分子。该研究不仅有助于理解HONO在矿物氧化物表面氧化SO_2的作用,而且为解释大气硫酸盐气溶胶的形成提供了理论依据。     

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.     

Low-temperature heat capacities,entropies and enthalpies of Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript> polymorphs,and α−β−γ and post-spinel phase relations at high pressure

The low-temperature isobaric heat capacities (C _p) of β- and γ-Mg₂SiO₄ were measured at the range of 1.8–304.7 K with a thermal relaxation method using the Physical Property Measurement System. The obtained standard entropies (S°₂₉₈) of β- and γ-Mg₂SiO₄ are 86.4 ± 0.4 and 82.7 ± 0.5 J/mol K, respectively. Enthalpies of transitions among α-, β- and γ-Mg₂SiO₄ were measured by high-temperature drop-solution calorimetry with gas-bubbling technique. The enthalpies of the α−β and β−γ transitions at 298 K (ΔH°₂₉₈) in Mg₂SiO₄ are 27.2 ± 3.6 and 12.9 ± 3.3 kJ/mol, respectively. Calculated α−β and β−γ transition boundaries were generally consistent with those determined by high-pressure experiments within the errors. Combining the measured ΔH°₂₉₈ and ΔS°₂₉₈ with selected data of in situ X-ray diffraction experiments at high pressure, the ΔH°₂₉₈ and ΔS°₂₉₈ of the α−β and β−γ transitions were optimized. Calculation using the optimized data tightly constrained the α−β and β−γ transition boundaries in the P, T space. The slope of α−β transition boundary is 3.1 MPa/K at 13.4 GPa and 1,400 K, and that of β−γ boundary 5.2 MPa/K at 18.7 GPa and 1,600 K. The post-spinel transition boundary of γ-Mg₂SiO₄ to MgSiO₃ perovskite plus MgO was also calculated, using the optimized data on γ-Mg₂SiO₄ and available enthalpy and entropy data on MgSiO₃ perovskite and MgO. The calculated post-spinel boundary with a Clapeyron slope of −2.6 ± 0.2 MPa/K is located at pressure consistent with the 660 km discontinuity, considering the error of the thermodynamic data.