Shear response of Fe-bearing MgSiO3 post-perovskite at lower mantle pressures

We investigate the shear response of possible slip systems activated in pure and Fe-bearing MgSiO₃ post-perovskite (PPv) through ab initio generalized stacking fault (GSF) energy calculations. Here we show that the [100](001) slip system has the easiest response to plastic shear among ten possible slip systems investigated. Incorporation of Fe²⁺ decreases the strength of all slip systems but does not change the plastic anisotropy style. Therefore, pure and Fe-bearing MgSiO₃ PPv should demonstrate similar LPO patterns with a strong signature of the [100](001) slip system. An aggregate with this deformation texture is expected to produce a V_SH > V_SV type polarization anisotropy, being consistent with seismological observations.     

The phase stability of Ca2TiO4 and related Ruddlesden–Popper phases

The Ruddlesden–Popper phases of the Ca–Ti–O system, Ca_n+1Ti_nO_3n+1, are investigated by means of atomistic simulations employing empirical pair potentials. The stability of the phases is examined in terms of various reaction schemes: the formation from the binary oxides, the addition of the perovskite oxide to a given phase, and the reaction between perovskite and rock-salt oxides. The energies of these reactions are compared with results previously obtained for the Ruddlesden–Popper phases of the Sr–Ti–O system. The importance of the disproportionation reaction of the various R–P phases in both Ca and Sr systems is also emphasized. The results obtained are in good agreement with experimental observations regarding both systems.     

Prediction of the phase transition from ferromagnetic perovskite to non-magnetic post-perovskite in SrRuO3 : A first-principles study

The phase transition in the perovskite (Pv) SrRuO₃ under pressure has been studied by using first-principles calculations based on density functional theory. The post-perovskite (Ppv) phase transition of SrRuO₃ will take place under hydrostatic pressure of about 40 GPa. The stability of Ppv- SrRuO₃ is justified by the enthalpy calculations, and this phase transition accompanies volume disconnection and magnetic moment collapses. The crystallographic data and the electronic structure of Ppv- SrRuO₃ are also predicted. The crystal structure of Ppv- SrRuO₃ is similar to that of Ppv- CaRuO₃. A non-magnetic ground state is found in Ppv- SrRuO₃. The strong hybridization of Ru and O is evident in the electronic structures of both phases. We expect that these results will help further understanding of SrRuO₃ under high pressure.     

Phase stability in the LnCa2Mn2O7 (Ln=Pr, Nd, Sm and Gd) Ruddlesden-Popper series

The synthesis of the Ruddlesden-Popper series, LnCa₂Mn₂O₇, (Ln=Pr, Nd, Sm and Gd) is described and their structure and electronic properties investigated. The reduction in size of the A-site cation causes an increase in the distortion of their orthorhombic structures (space group Cmcm). All of these compounds form with a perovskite impurity, the amount of which increases on reduction of the cation size. The synthesis temperature also alters the amount of perovskite impurity in the phase, but only to a lower limit, implying the perovskite phase is intrinsic to the material and that a phase equilibrium exists between the layered Ruddlesden-Popper and perovskite phases, which is controlled by the cation size. The magnetic susceptibility show transitions characteristic of the perovskite phase, therefore little direct information can be obtained about the Ruddlesden-Popper phases, except that ferromagnetism is not observed in any of these materials.     

Peierls–Nabarro model for dislocations in MgSiO3 post-perovskite calculated at 120 GPa from first principles

We present here the first numerical modelling of dislocations in MgSiO₃ post-perovskite at 120?GPa. The dislocation core structures and properties are calculated through the Peierls–Nabarro model using the generalized stacking fault (GSF) results as a starting model. The GSFs are determined from first-principle calculations using the VASP code. Dislocation properties such as planar core spreading and Peierls stresses are determined for the following slip systems: [100](010), [100](001), [100](011), [001](010), [001](110), [001](100), [010](100), [010](001), ½[110](001) and ½[110](110). Our results confirm that the MgSiO₃ post-perovskite is a very anisotropic phase with a plasticity dominated by dislocation glide in the (010) plane.     

First-principles study of the pressure-induced phase transition in CaTiO3

An investigation into the phase stabilities of CaTiO₃ under high pressure was conducted using first-principles calculations based on density functional theory. We have identified three candidate structures of CaTiO₃, Pbnm, Pm3m and Cmcm, respectively. Our results demonstrate that a phase transition from orthorhombic (Pbnm) to cubic (Pm3m) is impossible for CaTiO₃ under high pressure at ambient temperature, and further predict that Pbnm-CaTiO₃ will transform to post-perovskite phase (Cmcm) at enough temperature and pressure.     

Synthesis,photophysical properties,and photocatalytic applications of Bi doped NaTaO3 and Bi doped Na2Ta2O6 nanoparticles

Phase formation and photophysical properties of bismuth doped sodium tantalum oxide (perovskite, defect pyrochlore) nanoparticles prepared by a hydrothermal method were studied in detail. It was revealed that the synthesis conditions like NaOH concentration and bismuth precursor (NaBiO₃·2H₂O) markedly affect the crystal structure of sodium tantalum oxide. At low NaOH concentration and high bismuth precursor (NaBiO₃·2H₂O) content, Bi doped Na₂Ta₂O₆ (defect pyrochlore) phase was predominantly formed, while at higher NaOH concentration, Bi doped NaTaO₃ (perovskite) phase was formed. It was observed that the defect pyrochlore (Bi doped Na₂Ta₂O₆) phase was formed and stabilized by the presence of dopant precursor (NaBiO₃·2H₂O). The chemical analysis of the samples confirmed the doping of Bi³⁺ cations in both phases. Doping of bismuth enabled visible light absorption up to 500 nm in perovskite and defect pyrochlore type sodium tantalum oxide. Bi doped NaTaO₃ samples showed better performance for the photocatalytic degradation of rhodamine B than that of Bi doped Na₂Ta₂O₆, under visible light irritation (λ>420 nm). The present results shed light on phase formation of sodium tantalate and these results are useful in understanding properties of NaTaO₃ based compounds, synthesized by the hydrothermal method.     

On the criteria of formation and lattice distortion of perovskite-type complex halides

The famous Goldschmidt's tolerance factor gives us a necessary but not sufficient condition for the formation of perovskite-type compounds (ABX₃). In this work, computerized data analysis has been used to find some complementary criteria for the formation and lattice distortion of perovskite-type complex halides. It has been found that the radius ratio (R_A/R_X) and (R_B/R_X), affecting the stability of BX₆ octahedra and AX₁₂ cubo-octahedra (they are basic units of perovskite structure), are also dominating factors for the formation and lattice distortion of perovskite-type compounds. Besides, it has been found that the transition between the perovskite structure (with corner-sharing BX₆ octahedra) to BaNiO₃ structure (with face-sharing BX₆ octahedra) can be predicted by a criterion based on the relative magnitude of ionic radii and electronegativity. Based on multivariate data analysis, several complementary criteria for the formation and lattice distortion of perovskite-type complex halides have been obtained, and some empirical equations expressing the relationships between the ionic radii (R_A,R_B,R_X) and the lattice constants of perovskite-type complex halides have been found. The physical meaning of these empirical relationships has been discussed based on Pauling's rules of the crystal lattice stability of complex ionic compounds.     

Spreadsheets to calculate P–V–T relations,thermodynamic and thermoelastic properties of silicates in the MgSiO3–MgO system

Modified equations of state (EoS) of forsterite, wadsleyite, ringwoodite, akimotoite, bridgmanite and post-perovskite based on the Helmholtz free energy are described using Microsoft Excel spreadsheets. The equations of state were set up by joint analysis of reference experimental data and can be used to calculate thermodynamic and thermoelastic parameters and P–V–T properties of the Mg-silicates. We used Visual Basic for Applications module in Microsoft Excel and presented a simultaneous calculation of full set of thermodynamic and thermoelastic functions using only T–P and T–V data as input parameters. Phase transitions in the MgSiO₃–MgO system play an important role in the interpretation of the seismic boundaries of the upper Earth’s mantle and in the D″ layer. Therefore, proposed EoSes of silicates in the MgSiO₃–MgO system have clear geophysical implications. The developed software will be interesting to specialists who are engaged to study the mantle mineralogy and Earth’s interior.     

First-Principles Study of Orthorhombic Perovskites MgSiO3 up to 120 GPa and Its Geophysical Implications

High-pressure behaviour of orthorhombic MgSiO3 perovskite crystal is simulated by using the density functional theory and plane-wave pseudopotentials approach up to 120 GPa pressure at zero temperature. The lattice constants and mass density of the MgSiO3 crystal as functions of pressure are computed, and the corresponding bulk modulus and bulk velocity are evaluated. Our theoretical results agree well with the high-pressure experimental data. A thermodynamic method is introduced to correct the temperature effect on the O-K first-principles results of bulk wave velocity, bulk modulus and mass density in lower mantle PIT range. Taking into account the temperature corrections, the corrected mass density, bulk modulus and bulk wave velocity of MgSiO3-perovskite are estimated from the first-principles results to be 2%, 4%, and 1% lower than the preliminary reference Earth model （PREM） profile, respectively, supporting the possibility of a pure perovskite lower mantle model.     

Low-temperature property investigation of the lead indium-niobate-lead nickel-niobate solid solution

The complex perovskite solid solution (1−x) Pb(In_1/2Nb_1/2)O₃-(x) Pb(Ni_1/3Nb_2/3)O₃ has been successfully prepared by the Columbite precursor method. The temperature dependencies of the dielectric constant and pyroelectric coefficient were measured between −261 and 200 °C. Relaxor ferroelectric behavior has been noticed in all compositions across the solid solution. The room-temperature electrostrictive coefficient, Q₃₃, was 1.83×10⁻² C²/m⁴ for x=0.10. No room-temperature piezoelectric activity was detected; however, upon cooling to −261 °C the maximum coupling coefficients k_p=29%, k_t=11%, and k₃₃=31% were observed for the composition x=1.00.     

Synthesis and structural study of LaNi1−xMnxO3+δ perovskites

The synthesis of LaNi_1−xMn_xO_3+δ samples with different oxygen contents has been performed. Structural characterization was carried out by X-ray and neutron powder diffraction. The crystallographic structure of stoichiometric samples, δ=0, evolves from an orthorhombic (LaMnO₃) to a rhombohedral (LaNiO₃) unit cell. Oxygen excess, δ>0, seems to stabilize the rhombohedral unit cell. For instance, the unit cells at room temperature are orthorhombic and rhombohedral for LaNi_0.1Mn_0.9O_3.0 and LaNi_0.1Mn_0.9O_3.13, respectively. The X-ray patterns show the coexistence of both phases for LaNi_0.5Mn_0.5O_3+δ at room temperature. This coexistence is not ascribed to chemical inhomogeneities, but to a structural phase transition. Neutron patterns collected from 1.5 to 300 K show a continuous evolution except for LaNi_0.5Mn_0.5O_3.08 and LaNi_0.1Mn_0.9O_3.13, which show a phase transition at around 290 and 220 K, respectively. The neutron patterns suggest the presence of an ordered arrangement of Ni and Mn atoms in the crystallographic unit cell. Such arrangement indicates that LaNi_0.5Mn_0.5O₃ could be considered as a double perovskite (nominal formula, La₂NiMnO₆).     

Densification, microstructural evolution, and dielectric properties of CaTiO3-LaGaO3 microwave ceramics

The relations among the densification, microstructural evolution, and microwave dielectric properties of the (1−x)CaTiO₃-xLaGaO₃ ceramics with x=0.34 and 0.36 were investigated in this study. The results indicated that (1−x)CaTiO₃−xLaGaO₃ ceramics can be densified at 1300 °C with at least 97% of the theoretical value. The ceramics reported an orthorhombic perovskite structure, and no other detectable phases were found. Both ε_r and Q×f values can be improved by slowing the cooling rate during sintering. The ε_r and Q×f values of the 0.64CaTiO₃-0.36LaGaO₃ ceramics at cooling rates of >10 °C/min and 0.1 °C/min are 48.1 and 27,500 and 48.7 and 38,000, respectively. The higher densification obtained at a slower cooling rate plays an important role in improving the microwave dielectric properties.     

Crystallographic and magnetic structures of Y0.8Sr2.2Mn2GaO8−δ: a new vacancy-ordered perovskite structure

The anion-deficient perovskite Y_0.8Sr_2.2Mn₂GaO_8−δ (where δ∼0.1) has been synthesised and the crystal and magnetic structures determined by Rietveld analysis of neutron powder diffraction (NPD) data. The material has body-centred tetragonal symmetry (I4/mmm, a=7.6373(3) Å and c=15.6636(10) Å) and consists of alternating layers of octahedral and tetrahedral polyhedra, the layers being perpendicular to [001]. The octahedral layers are preferentially occupied by manganese and the tetrahedral layers are a mixture of manganese and gallium. The precise cation distribution depends critically on preparative conditions. An unusual structural feature of these materials is the arrangement of oxygen vacancies in the tetrahedral layers: in the basic structure, isolated squares of corner-linked tetrahedra are formed instead of the chains that are observed in brownmillerite phases. Additional oxide ions in this layer probably allow the Mn ions to achieve distorted square pyramidal coordination. Low temperature NPD and magnetisation data indicate antiferromagnetic ordering below 100 K.     

下地幔硅酸盐矿物的结构和电子相变对其高压下光学性质的影响

基于第一性原理平面波超软赝势法并结合局域密度近似,计算了(Mg_(0.875),Fe_(0.125))SiO_3钙钛矿和(Mg_(0.9),Fe_(0.1))SiO_3后钙钛矿晶体在高压下的光学性质.计算数据表明:(1)钙钛矿的结构相变将导致其吸收性增强,证实了基于实验数据的推断.(2)后钙钛矿二价铁吸收带的波数位置与实验观测结果相近.(3)在后钙钛矿相区,压力将导致吸收带的强度缓慢增加,但二价铁自旋态的转变对其吸收谱的影响却非常微弱.(4)钙钛矿的结构相变将导致其折射率升高;在后钙钛矿相区,压力及自旋态转变对折射率的影响不明显.(5)波数大约在12500 cm~(-1)以下,后钙钛矿折射率随波数的增加而降低,钙钛矿的折射率则变化不大;波数大约在12500 cm~(-1)以上,钙钛矿折射率随波数的增加而增大,后钙钛矿的折射率则显著上升.     

硅酸镁钙钛矿弹性及热力学特性的第一性原理计算

基于密度泛函理论的第一性原理计算,结合准谐德拜模型研究了高压下硅酸镁钙钛矿的弹性及热力学特性. 计算得到的物态方程数据、热容、热膨胀系数等在宽广的温度和压力范围与实验结果及其他理论计算结果吻合. 根据有限应变理论计算了硅酸镁钙钛矿的弹性常数,并讨论了杨氏模量、泊松比、德拜温度、晶体各向异性随压力的变化.     

Structure and magnetic properties of perovskite Sr2CuNbO6−δ

Single phase perovskite Sr₂CuNbO_6−δ with a high proportion of Cu¹⁺ ions and oxygen vacancies was synthesized by solid-state reaction. The structure was determined by Rietveld method with space group Pm3m. Isotropic g value was evaluated from electron spin resonance (ESR) measurements. The ESR result is consistent with that of magnetic susceptibility.     

Study of the structural, dielectric and magnetic properties of Bi2O3 and PbO addition on BiFeO3 ceramic matrix

In this paper we studied the effects of Bi₂O₃ and PbO addition on BiFeO₃ (BFO) ceramic matrix. The structural, dielectric and magnetic properties of fifteen BFO samples were discussed in view of possible applications in RF and microwave devices. The present work also reports the preparation of the samples. Polyvinyl alcohol (PVA) and tetraethyl orthosilicate (TEOS) were also added as a binder in the fabrication procedure. The samples have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and magnetic hysteresis measurements. Further, a study based on impedance spectroscopy also has been done. Dielectric permittivity (ε′) and dielectric loss (tan δ) were measured at room temperature in the frequency range 100 Hz-10 MHz, as well as a.c. conductivity. The -Im[Z(f)] versus Re[Z(f)] plot has been obtained. The samples were investigated in view of possible applications like miniaturized filters, diplexers and dielectric resonator antennas (DRA). In the RF and MW frequency region, the application of magneto-dielectric and multiferroic perovskite composite materials is desirable for the miniaturization of components.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Structural, electronic properties and stability of tungsten mono- and semi-carbides: A first principles investigation

First principles calculations have been performed with the purpose to understand the comparative peculiarities of the structural, electronic properties and stability for all phases formed in the tungsten-carbon system: hexagonal and cubic mono-carbides WC and four polymorphs (α, β, γ and ε) of semi-carbide W₂C. All calculations were performed by means of the full-potential linearized augmented plane wave method (FLAPW). The generalized gradient approximation (GGA) in the Perdew-Burke-Ernzerhof (PBE) formalism was used for the exchange and correlation energy functional. The geometries of all WC and W₂C phases were optimized and their structural parameters and theoretical density were established. Besides, we have evaluated the formation energies (E_form) of all the tungsten carbides. Based on our estimations we can arrange all investigated W-C phases depending on their stability in the following sequence: h-WC>ε-W₂C>β-W₂C>γ-W₂C>α-W₂C>c-WC. Here three carbides (h-WC, ε-W₂C and β-W₂C) are stable (E_form<0), γ-W₂C belongs to metastable systems (E_form∼0), whereas α-W₂C and c-WC appear to be unstable (E_form>0). Moreover, band structures, total and partial densities of states were obtained and analyzed systematically for all W-C phases in comparison with other available theoretical and experimental data.