Theoretical prediction of the elastic properties of body-centered cubic Fe-Ni-Mg alloys under extreme conditions

Using density functional theory formulated within the framework of the exact muffin-tin orbital method, we investigate the elastic properties of the body-centered cubic Fe_0.85Ni_0.1Mg_0.05 alloy in the conditions at the Earth's inner core. We demonstrate that in this system, the chemical stabilization effect of Mg is significantly larger than that of Ni. We show that the elastic properties of Fe_0.85Ni_0.1Mg_0.05 are in good agreement with those of the Earth's inner core, as given by seismic observations. We find that the excellent mechanical properties of Fe_0.85Ni_0.1Mg_0.05 are primarily due to Mg.     

High-spin-low-spin transition in magnesiowüstite (Mg<Subscript>0.75</Subscript>,Fe<Subscript>0.25</Subscript>)O at high pressures under hydrostatic conditions

The spin states of Fe²⁺ ions in (Mg_0.75,Fe_0.25)O magnesiowüstite crystals at hydrostatic pressures up to 90 GPa created in a diamond-anvil cell with helium as a pressure-transmitting medium have been investi-gated by transmission and synchrotron Mössbauer spectroscopy at room temperature. An electron transition from the high-spin (HS) state to the low-spin (LS) state (HS-LS crossover) has been observed in the pressure range of 55–70 GPa. The true HS-LS transition occurs in a narrow pressure range and the extension of the electron transition to ～15 GPa is attributed to the effect of the nearest environment and to thermal fluctuations between the high-spin and low-spin states at finite temperatures. It has been found that the lowest pressure at which the electron HS-LS transition can occur in the Mg_{1 ? x} Fe _x system is 50–55 GPa.     

Development of an energy‐domain 57Fe‐Mössbauer spectrometer using synchrotron radiation and its application to ultrahigh‐pressure studies with a diamond anvil cell

An energy‐domain ⁵⁷Fe‐Mössbauer spectrometer using synchrotron radiation (SR) with a diamond anvil cell (DAC) has been developed for ultrahigh‐pressure measurements. The main optical system consists of a single‐line pure nuclear Bragg reflection from an oscillating ⁵⁷FeBO₃ single crystal near the Néel temperature and an X‐ray focusing device. The developed spectrometer can filter the Doppler‐shifted single‐line ⁵⁷Fe‐Mössbauer radiation with a narrow bandwidth of neV order from a broadband SR source. The focused incident X‐rays make it easy to measure a small specimen in the DAC. The present paper introduces the design and performance of the SR ⁵⁷Fe‐Mössbauer spectrometer and its demonstrative applications including the newly discovered result of a pressure‐induced magnetic phase transition of polycrystalline ⁵⁷Fe₃BO₆ and an unknown high‐pressure phase of Gd⁵⁷Fe₂ alloy placed in a DAC under high pressures up to 302 GPa. The achievement of Mössbauer spectroscopy in the multimegabar range is of particular interest to researchers studying the nature of the Earth's core.     

Stress‐induced Curie temperature increase in the Fe64Ni36 invar alloy

Structural and magnetic changes on invar Fe₆₄Ni₃₆ alloy (T_C = 500 K) produced by mechanical milling followed by heating up to 1073 K, were investigated by neutron diffraction, magnetization measurements, X‐ray diffraction under high pressures and X‐ray absorption at both Fe and Ni K‐edges. We argue that the strain induced in the Fe₆₄Ni₃₆ material after this treatment mainly affects the Fe sites due to the magnetovolume coupling, the most notorious feature being the increase of the Curie temperature (ΔT_C = 70 K). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of high-performance Fe–Mg-co-doped LiMnPO<Subscript>4</Subscript>/C via a mechano-chemical liquid-phase activation technique

Carbon-coated Fe–Mg-homogeneously dispersed Li(Mn_0.9Fe_0.10)_1???x Mg _x PO₄/C (x?=?0.00, 0.01, 0.03, 0.05, and 0.07) powders are synthesized via a mechano-chemical liquid-phase activation technique. Fine-sized and Fe²⁺ and Mg²⁺ evenly distributed precursors are formed using this efficient approach successfully. The synthesis temperature and the Mg²⁺ doping ratio are investigated and optimized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electrochemical measurements. Mg doping decreases the lattice parameters of LiMn_0.9Fe_0.1PO₄/C, which will ease the expansion/shrinking effect during the insertion/de-insertion processes. Li(Mn_0.9Fe_0.1)_0.95Mg_0.05PO₄/C synthesised at 700 °C with ~3 wt% of carbon additive presents the best comprehensive electrochemical properties, and it displays good rate capability with specific discharge capacity of 153 mAh g^?1 at 0.1C, 140 mAh g^?1 at 1C, and 132 mAh g^?1 at 2C rate. The results suggest that the electrochemical performance of the LiMnPO₄-based cathode is improved as (Mn_0.9Fe_0.1) is partially substituted by Mg.     

(Fe0.1Co0.55Ni0.35)78Si8B14金属玻璃的晶化过程及压力的影响(Ⅰ)——晶化时的相析出过程

用X射线衍射法研究了(Fe_0.1Co_0.55Ni_0.35)₇₈Si₈B₁₄金属玻璃在常压下及20kbar高压下晶化过程中的析出相及析出过程。结果表明在上述压力下晶化过程都分成两个阶段,分别对应于初级晶化和共晶晶化。在常压下,初级晶化时析出fcc-Co晶体,而共晶晶化对应着Ni₃₁Si₁₂和(FeCoNi)₃(SiB)相的析出。随着回火温度的增高或时间的延长,(FeCoNi)₃(SiB)相逐渐转变为(FeCoNi)₂₃B₆相。20kbar高压下的晶化析出过程与常压下不同的是:提高了晶化温度,在共晶晶化阶段出现了Co₂B相。此外,压力还阻止(FeCoNi)₂₃B₆相的形成。从热力学和动力学的角度讨论了压力对金属玻璃晶化过程的影响。 关键词：     

Magnetic and Mössbauer study of Mg0.9Mn0.1Cr x Fe2−x O4 ferrites

The ferrites Mg_0.9Mn_0.1Cr _x Fe_2?x O₄ ( The ferrites Mg_0.9Mn_0.1Cr _x Fe_2−x O₄ () were prepared using the conventional double sintering method. The XRD showed that the samples maintain a single spinel cubic phase. The M?ssbauer measurements were carried out at room and liquid nitrogen temperatures. From the area ratios of the A and B sites, it was found that the Fe cation population of the A and B sites decreases in proportion to Cr concentration. The contact hyperfine fields at the A and B sites were found to decrease with increasing Cr contents. This was found to be in approximate agreement with the results of magnetization measurement. The distributions of Mg and Mn cations versus Cr concentration were also determined using the M?ssbauer and magnetization results. The Curie temperatures were determined and found to agree with the reported values. As the Cr contents increases the relative magnetization, was found to increase at low temperatures and decreases at higher temperatures.     

Mössbauer study of the re-entrant spin-glass behaviour in the mixed spinel ferrites Mg(0.9+x)Fe2(1−x)Ni0.1TixO4 (x=0.5 and 0.6)

Samples of the mixed spinel ferrite series Mg_(0.9+x)Fe_2(1−x)Ni_0.1Ti_xO₄ with x=0.5 and 0.6, prepared by solid state reaction of the appropriate oxides, have been investigated with ⁵⁷Fe Mössbauer spectroscopy. The as-prepared samples are found to be mainly superparamagnetic due to magnetic cluster formation. Samples after at least three times reheated exhibit spectra, which can be rather interpreted by a transversal relaxation of the spin above and spin-glass behaviour below the respective freezing temperatures T_f. External-field spectra reveal the canting to occur only on the octahedral sites. From the derived transition temperatures and thresholds together with data from earlier investigated sample with x=0.7 a compositional magnetic phase diagram for this spinel series is obtained.     

Optimization of the conditions of synchrotron Mössbauer experiment for studying electronic transitions at high pressures by the example of (Mg, Fe)O magnesiowustite

The effect of the experimental conditions on the shape of the nuclear resonant forward scattering (NFS) from (Mg_0.75Fe_0.25)O magnesiowustite has been studied at high pressures up to 100 GPa in diamond anvil cells by the method of the NFS of synchrotron radiation from the Fe-57 nuclei at room temperature. The behavior of the system in the electronic transition of the Fe²⁺ ion from the high-spin to low-spin state (spin crossover) near 62 GPa is analyzed as a function of the sample thickness, degree of nonhydrostaticity, and focusing and collimation conditions of a synchrotron beam. It is found that the inclusion of dynamical beats associated with the sample thickness is very important in the approximation of the experimental NFS spectra. It is shown that the electronic transition occurs in a much narrower pressure range (±6 GPa) rather than in a broad range as erroneously follows from experiments with thick samples under strongly nonhydrostatic conditions.     

Synthesis and electrical characterisation of different doped magnesium titanates

The synthesis and characterization are reported for the cubic spinel titanate Mg_(2−x)Ni_xTiO₄ (x≤0.25) and Mg_(2−x)Mn_xTiO₄ (x≤1). Single phase samples were observed for Mg_(2−x)Ni_xTiO₄ and with x≤0.4 for Mg_(2−x)Mn_xTiO₄. AC measurements were carried out on four different compositions (x=0.01, 0.03, 0.04 and 0.15) in the Mg_(2−x)Ni_xTiO₄ series and for Mg_1.9Mn_0.1TiO₄. For all these compounds, increasing conductivity with temperature and Arrhenius conductivity dependence are observed, the activation energy is around 0.28 eV for the Ni compounds and is 0.184 eV for Mg_1.9Mn_0.1TiO₄. The DC conductivity was recorded over a range of oxygen partial pressures (10⁻¹⁹ to 1 atm) at 930 °C. The Mg_(2−x)Ni_xTiO₄ compounds show a n-type behaviour whereas the Mg_(2−x)Mn_xTiO₄ show a p-type behaviour at high p(O₂) and n-type at low p(O₂). The stability under reduced conditions was checked and discussed for the different synthesized compounds. Paper presented at the 5th Euroconference onSolid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Fe2+取代对MgSiO3钙钛矿高温高压物性的影响

(Mg, Fe)SiO₃钙钛矿是下地幔中最主要的候选矿物成分之一, 关于其高温高压特性的研究对于深层地幔状态的理解和地震波变化规律的探索具有重要意义. 应用第一性原理计算了MgSiO₃和(Mg_0.75, Fe_0.25)SiO₃在0–140 GPa静水压范围内的晶体结构和弹性模量, 并由Voigt-Reuss-Hill方程计算了地震波速随压力的变化, 利用准简谐近似下的Debye模型模拟了高温效应, 分析了Fe²⁺取代Mg²⁺后镁铁钙钛矿弹性和热学性质的变化, 推断Fe²⁺取代行为软化了MgSiO₃等含镁的地球深部矿物的地震波速. 为解释地幔中某些区域的地震波速软化现象提供了一个有力的理论依据. 关键词： 钙钛矿 铁 高压 波速     

In situ energy dispersive X-ray diffraction study of iron disilicide thermoelectric materials

The dynamic phase transformation and structure of rapidly solidified Fe_1−xCo_xSi₂ (0.02?x?0.06) thermoelectric materials were in situ investigated under high temperatures and high pressures by energy dispersive X-ray diffraction using synchrotron radiation. The FeSi₂ alloys which solidified as α-Fe₂Si₅ and ε-FeSi eutectic structures, were transformed to the semiconducting β-FeSi₂ phase upon heating by the main reaction α+ε→β and the subsidiary reaction α→β+Si. The low heating rates and Co contents were found to be beneficial for the β phase formation. The decomposition temperature of β→α+ε was weakly dependent on heating rate, but significantly suppressed by the high pressures.     

Synthesis and high-frequency magnetic properties of sol–gel derived Ni–Zn ferrite–forsterite composites

Ni_0.5Zn_0.5Fe₂O₄–forsterite composites were synthesized by a sol–gel method. X-ray diffraction and SEM were used to characterize the crystallization behavior of the composite samples which were heat treated at temperatures varying from 800 to 1100°C. The results showed that Ni_0.5Zn_0.5Fe₂O₄ and forsterite (Mg₂SiO₄) can co-crystallize and the crystallites grow even more larger with increasing heat-treatment temperature. High-frequency (10 MHz–1 GHz) magnetic and dielectric properties of the composite samples were presented. Permeability increased with heat-treatment temperature. Quality factor was found to be two orders higher than that of equivalent pure, bulk ferrite.     

Range of homogeneity and defect interaction in high temperature nickel sulfide Ni1−xs

Sulphur pressures were measured directly and indirectly (H₂S/H₂) inside and adjacent to the homogeneity range of Ni_1?xS. The results give direct evidence of the boundaries of the homogeneity range and can be interpreted in terms of metal vacancy formation and interaction. Interstitial metal atoms could not be detected (in contrast to Fe_1?xS). Ni_1?xS melts congruently at 1265 K under a total sulphur pressure of about 24 atm at a composition of 51.96 ±0.1 atomic per cent S.     

High-pressure Mössbauer spectroscopy using synchrotron radiation and radioactive sources

A high-pressure ⁵⁷Fe Mössbauer study of SrFeO₃ up to 74 GPa has been performed with diamond-anvil-cell (DAC) using synchrotron radiation and a radioactive point source of ⁵⁷Co in Rh. SrFeO₃ is known as a typical cubic perovskite with a high-valence state of Fe⁴⁺ and shows metallic conductivity at 0.1 MPa down to 4.2 K. Applying an external high pressure, SrFeO₃ has not shown any structural transformation up to 74 GPa keeping an Fe⁴⁺ state but the Néel temperature increases up to 300 K at 18 GPa. The external high pressure may induce the ferromagnetism in SrFeO₃ by a decrease of the interatomic distance of Fe or an increase of the d-band width. ⁵⁷Fe Mössbauer measurements under externally applied longitudinal magnetic field using radioactive ⁵⁷Co in Rh source and also nuclear forward scattering measurements with a linearly polarized synchrotron radiation under external magnetic field indicate the existence of the pressure induced ferromagnetism in SrFeO₃. In this work we compare high-pressure Mössbauer spectroscopy using synchrotron and radioactive sources and summarize the advantages and disadvantages of each method.     

A comparative study of FMR and Brillouin light scattering on amorphous Fe40Ni40B20

It is shown that magnetic surface mode frequencies in the amorphous ferromagnet Fe₄₀Ni₄₀B₂₀ measured using Brillouin light scattering depend upon the incident laser light intensity: presumably due to local heating of the specimen due to the concentration of the light flux into a focal spot only a few microns in diameter. Surface mode frequencies extrapolated to zero light intensity are shown to be consistent with magnetic parameters measured using ferromagnetic resonance at 35.731 GHz to within ±0.5 GHz for specimens of amorphous Fe₄₀Ni₄₀B₂₀. 0.5 GHz corresponds to a change of 0.17 kG in the saturation magnetization, 4πM_s.     

Fabrication of p-type ZnMgO films via pulsed laser deposition method by using Li as dopant source

p-Type Zn_0.9Mg_0.1O thin films have been realized via monodoping of Li acceptor by using pulsed laser deposition. The Li-doped Zn_0.9Mg_0.1O thin films possessed a good crystallinity with a (0 0 0 2) preferential orientation and a high transmittance in the visible region. Secondary ion mass spectroscopy revealed that Li has been successfully incorporated into the Zn_0.9Mg_0.1O films. The obtained films with the best electrical properties show a hole concentration in the order of 10¹⁷ cm⁻³ and a room-temperature resistivity in the range of 58-72 Ω cm.     

Mössbauer study of Mg–Ni(Fe) alloys processed as materials for solid state hydrogen storage

Mg–Ni–Fe magnesium-rich intermetallic compounds were prepared following two distinct routes. A Mg₈₈Ni₁₁Fe₁ sample (A) was prepared by melt spinning Mg–Ni–Fe pellets and then by high-energy ball milling for 6 h the obtained ribbons. A (MgH₂)₈₈Ni₁₁Fe₁ sample (B) was obtained by high-energy ball milling for 20 h a mixture of Ni, Fe and MgH₂ powders in the due proportions. A SPEX8000 shaker mill with a 10:1 ball to powder ratio was used for milling in argon atmosphere. The samples were submitted to repeated hydrogen absorption/desorption cycles in a Sievert type gas–solid reaction controller at temperatures in the range 520?÷?590 K and a maximum pressure of 2.5 MPa during absorption. The samples were analysed before and after the hydrogen absorption/desorption cycles by X-ray diffraction and Mössbauer spectroscopy. The results concerning the hydrogen storage properties of the studied compounds are discussed in connection with the micro-structural characteristics found by means of the used analytical techniques. The improved kinetics of hydrogen desorption for sample A, in comparison to sample B, has been ascribed to the different behaviour of iron atoms in the two cases, as proved by Mössbauer spectroscopy. In fact, iron results homogeneously distributed in sample A, partly at the Mg₂Ni grain boundaries, with catalytic effect on the gas–solid reaction; in sample B, instead, iron is dispersed inside the hydride powder as metallic iron or superparamagnetic iron.     

Magnetic properties of Nd0.9Dy0.1Fe3(BO3)4

The magnetic properties of trigonal Nd_0.9Dy_0.1Fe₃(BO₃)₄ substituted compound with the competitive Nd-Fe and Dy-Fe exchange interactions have been investigated. It has been shown that in Nd_0.9Dy_0.1Fe₃(BO₃)₄ a spontaneous spin-reorientation transition from an ease-axis state to an easy-plane occurs near 8 K. Anomalies of the magnetization curves are observed in a spin-flop transition induced by the magnetic field B‖c. The calculations were performed using a molecular-field approximation and a crystal-field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of Nd_0.9Dy_0.1Fe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences.     

The Kinetics of the Cd21Ni5 Intermetallic Growth under High Hydrostatic Pressure

The kinetics of growth of the Cd₂₁Ni₅ intermetallic phase in two-layer Cd-Ni samples has been studied at hydrostatic pressures 0.05–0.9 GPa and at temperatures 200–280°C. Arrhenius equations for both interdiffusion through the growing phase layer and the interfacial reaction have been obtained for different pressures. The activation volumes have been found to be 0.9V₀ for interdiffusion and 1.6V₀ for interfacial reaction, where V_{_0} 1.8 × 10_-29m₃ is the average volume per atom in the Cd₂₁Ni₅ lattice. Atomistic mechanisms of intermetallic growth are discussed.