Structural,magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

At ambient pressure CaFe₂As₂ has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ～ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ～0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ～1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe₂As₂ transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.     

Characterization of iron nitrides prepared by spark erosion,plasma nitriding,and plasma immersion ion implantation

The effect of the nitrogen uptake in α-iron upon spark erosion in gaseous and liquid ammonia, plasma nitriding, and plasma immersion ion implantation is studied. The resulting phases and hyperfine parameters, measured by the Mössbauer spectroscopy, are discussed from the point of view of initial conditions of their preparation and subsequent heat and/or mechanical treatment. Spark erosion in the ammonia gas produces fine particles with the dominating ferromagnetic α-Fe phase (50%). The 20% of specimen volume form α′-Fe and α′′-Fe₁₆N₂ phases. The last 30% occupy the γ′-Fe₄N, ferro- and paramagnetic ε phases, and γ-Fe(N). Nitriding in the liquid ammonia allows to incorporate the higher content of nitrogen into α-iron particles which results in the formation of paramagnetic ε(ζ)-Fe₂N phase. This phase also dominates the surface of α-iron specimen implanted by nitrogen using plasma immersion ion implantation at 300°C/3 h, where high uptake of nitrogen (approx. 30 at%) is reached. Plasma nitriding at 510°C results in the formation of γ′-Fe₄N phase.     

Phase transition and optoelectronic properties of MgH2

In this article, structural and electronic properties of MgH₂ have been studied. The aim behind this study was to find out the ground state crystal structure of MgH₂. For the purpose, density functional theory (DFT)-based full-potential linearized augmented plane wave (FP-LAPW) calculations have been performed in three different space groups: P4₂/mnm (α-MgH₂), Pa3 (β-MgH₂) and Pbcn (γ-MgH₂). It has been found that the ground state structure of MgH₂ is α-MgH₂. The present study shows that α-MgH₂ transforms into γ-MgH₂ at a pressure of 0.41 GPa. After further increase in pressure, γ-MgH₂ transforms into β-MgH₂ at a pressure of 3.67 GPa. The obtained results are in good agreement with previously reported experimental data. In all the studied phases, the behavior of MgH₂ is insulating and its optical conductivity is around 6.0 eV. The α-MgH₂ and γ-MgH₂ are anisotropic materials while β-MgH₂ is isotropic in nature.     

Phase dependent photoluminescence and energy transfer in Ca2P2O7: Eu2+, Mn2+ phosphors for white LEDs

α- and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ phosphors were prepared by solid-state reaction. Phase transition from tetragonal (β-phase) to monoclinic (α-phase) is performed. A strong orange emission of Mn²⁺ is observed in both α-and β-Ca₂P₂O₇: Eu²⁺, Mn²⁺ upon near ultraviolet (UV) excitation through energy transfer from Eu²⁺ to Mn²⁺. The transfer efficiencies for various Mn²⁺ concentrations are estimated based on lifetime measurements of the fluorescence of Eu²⁺ in the two phases. The photoluminescence excitation spectra of α-Ca₂P₂O₇: Eu²⁺, Mn²⁺ can cover 400 nm of the near-UV range, denoting its potential use as a phosphor with intense orange component for white light emitting diodes (LEDs).     

Pressure-induced magnetic transition in MnRhAs

The magnetic properties of a Fe₂P-type intermetallic compound MnRhAs have been investigated under high pressure up to 8.0 GPa by AC susceptibility measurement. Initially, both the antiferromagnetic (AF(I)) to the canted state magnetic transition temperature T_t and the canted state to another antiferromagnetic one (AF(II)) transition temperature T_C increase with compression. At 4.0 GPa, however, T_t decreases abruptly, while the increasing rate of T_C becomes larger above this pressure. A pressure-induced magnetic phase transition was seen at around this pressure when T_t and T_C are plotted in the pressure–temperature phase diagram. The transition from the antiferromagnetic to the ferromagnetic state observed below 160 K with increasing pressure is not frequently observed.     

Behavioral response of pyrite structured Co0.2Fe0.8S2 nano-wires under high-pressure up to 8 GPa – Mössbauer spectroscopic and electrical resistivity studies

Pyrite-structured Co_0.2Fe_0.8S₂ nano wires with aspect ratio 45:1, synthesized using solution colloid method were studied under high pressure up to 8 GPa using ⁵⁷Fe Mössbauer spectroscopy (using diamond anvil cell) and electrical resistivity (using tungsten carbide cell) techniques. Room temperature S K-edge XANES studies at INFN-LNF synchrotron beam line signified the changes in the electronic structure owing to Co substitution. Magnetic measurements at 5 K demonstrated disordered ferromagnetic behavior similar to Griffith phase. The value of isomer shift identified Fe in divalent, low spin state corresponding to pyrite structure. Higher value of quadrupole splitting observed at ambient condition was due to large lattice strain and electric field gradient generated by large surface to volume ratio of the nano size of the system. With applied pressure, the value followed the expected trend of increase up to 4.3 GPa, then to decrease till 6.4 GPa. Such change in the trend suggested a phase transition. On decompression to ambient pressure, the system seemed to retain high pressure phase and nano structure. The pressure coefficient of electrical resistivity varying from −0.0454 to −0.166 Ω-cm/GPa across the transition pressure of ~4.5 GPa was sluggish suggesting second order phase transition. The pressure-dependent variations by Mössbauer parameters and electrical resistivity showed identical result. This is the first report of pressure effect on nano sized Co_0.2Fe_0.8S₂. Effect of particle size on transition pressure could not be evaluated due to lack of available reports on bulk system.     

First-principles investigation on high-pressure structural evolution of MnTiO3

First-principle calculations using density-functional theory with linearized augmented plane wave method and projector-augmented method have been performed for the high-pressure MnTiO₃ polymorphs and their possible dissociation products. Theoretical results demonstrate that ilmenite-type MnTiO₃ transforms into perovskite phase at 27 GPa and 0 K. The lithium niobate phase of MnTiO₃ is confirmed to be metastable according to its higher Gibbs free energy compared with that of ilmenite at ambient conditions. In ilmenite and lithium niobate phases, MnO₆ octahedra become more distorted while TiO₆ octahedra become more regular with increasing pressure. In orthorhombic perovskite phase, the structural distortion deviated from the ideal cubic perovskite is enhanced at higher pressure. Based on the non-spin-polarized calculations, perovskite phase MnTiO₃ is predicted to dissociate into Fm3?m-MnO+P2₁/c-MnTi₂O₅ at 29 GPa.     

Theoretical investigation of the electronic structure and structural phase stability of CeGa2 under pressure

Recently, Chandra Shekar et al. (Phys. Stat. Sol. B 241(2004)2893), studied the structural stability of CeGa₂ under high pressure up to ∼32 GPa and reported a structural transition from hexagonal AlB₂-type to omega trigonal-type starting at ∼16 GPa with a volume collapse of ∼6%. The high-pressure omega triginal phase is found to coexist with the parent phase up to 32 GPa. In this paper, we report the results of our band structure calculations on this system as a function of reduced volume by the tight-binding linear muffin–tin orbital (TB-LMTO) method, in order to look into this structural transition and to understand it in terms of changes in its electronic structure. Our calculations indicate a structural transition at ∼30.6 GPa with a volume collapse of 3.5%, in good agreement with the experimental results. The possible mechanism of the phase transition may be due to f→d electron transfer under pressure. The theoretically calculated ground-state properties, namely the lattice parameters and the bulk modulus are also in good agreement with the experimental values.     

Structure dependent luminescence characterization of green–yellow emitting Sr2SiO4:Eu2+ phosphors for near UV LEDs

This paper reports on the luminescence properties of mixtures of α- and β-(Sr_0.97Eu_0.03)₂SiO₄ phosphors. These phosphors were prepared by 3 different synthesis techniques: a modified sol–gel/Pechini method, a co-precipitation method and a combustion method. The structural and optical properties of these phosphors were compared to those of solid state synthesized powders. The emission spectra consist of a weak broad blue band centered near 460 nm and a strong broad green–yellow band centered between 543 and 573 nm depending on the crystal structure. The green–yellow emission peak blue-shifts as the amount of β phase increases and the photoluminescence emission intensity and quantum efficiency of the mixed phase powders is greater than those of predominant α-phase powders when excited between 370 and 410 nm. Thus, (Sr_1?xEu_x)₂SiO₄ with larger proportion of the β phase are more promising candidates than single α-phase powders for use as a green–yellow emitting phosphor for near UV LED applications. Finally the phosphors prepared by the sol–gel/Pechini method, which have larger amount of β phase, have a higher emission intensity and quantum efficiency than those prepared by co-precipitation or combustion synthesis.     

Quantum dots of Cd0.5Mn0.5Te semimagnetic semiconductor formed by the cold isostatic pressure method

Cd_0.5Mn_0.5Te is a semimagnetic semiconductor, which crystallizes in the zinc-blende structure (ZB) and exhibits a magnetic spin glass like transition at 21 K. Under pressure it shows a first-order phase transition around 2.6 GPa to the NaCl like structure. In this work, the pressure cycled method using a Paris–Edinburgh cell up to 8 GPa has been applied to Cd_0.5Mn_0.5Te samples in order to obtain recovered nanocrystals. The nanoparticles have been characterized by EDX and electron microscopy. The X-ray and electron diffraction results confirmed the existence of nanocrystals in the ZB phase with an average size of 7 nm. Magnetization measurements made in the range of 2–300 K at low field show that the temperature of the magnetic transition decreases when the crystallites’ size is reduced.     

Structure,magnetic and microwave properties of FeNi invar nanoparticles obtained by electrical explosion of wire in different preparation conditions

Magnetic nanoparticles (MNPs) of close to invar (Fe_0.635Ni_0.365) composition were prepared by the electrical explosion of wire using different conditions to insure different values of overheating rates. X-ray diffraction, transmission electron microscopy, low temperature nitrogen adsorption, magnetic and microwave measurements were used for the characterization of MNPs. Increase of the energy injected into the wire led to increase of the specific surface (S_sp) of the produced MNPs from 4.6 to 13.5 m²/g. The fabricated MNPs were spherical and weakly aggregated with the average weighted diameter in the range of 54–160 nm depending on the S_sp. The phase composition of FeNi MNPs consists of two solid solutions of Ni in α-phase and γ-phase lattices. The increase of the energy injected into the wire leads to increase of the α-phase from 5 to 10 wt% as the injected energy raised from 0.8 to 2.5 times the sublimation energies of the wire material. Comparative analysis of structure magnetic and microwave properties showed that the obtained MNPs are important magnetic materials with high saturation magnetization and significant zero field microwave absorption which can be expected to lead to important technological applications.     

Structural and magnetic properties of chromium dioxide at high pressures

Ab initio calculations were performed on CrO₂ to study its behavior and possible similarity to silica under high pressures. At the rutile→CaCl₂-type phase transition, the lattice constants, cell volume and total energy change continuously, indicating the second-order nature of the phase transition, consistent with the experimental observations. The current calculations have demonstrated that the rutile→CaCl₂-type phase transition is driven by the softening of the Raman active B_1g mode, weakly coupling with the elastic shear modulus C_s. Further phase transitions of CrO₂ to denser packed phases of α-PbO₂-type and pyrite have been well predicted by total energy calculations. Our electronic calculations revealed that CrO₂ is still a half-metallic ferromagnet up to pressure of 95 GPa. The present results confirm the analogy of the phase sequence between silica and CrO₂ at high pressures.     

Pressure-induced variation of structural,elastic, vibrational,electronic, thermodynamic properties and hardness of Ruthenium Carbides

Three of the five structures obtained from the evolutionary algorithm based structure search of Ruthenium Carbide systems in the stoichiometries RuC, Ru₂C and Ru₃C are relaxed at different pressures in the range 0–200 GPa and the pressure-induced variation of their structural, elastic, dynamical, electronic and thermodynamic properties as well as hardness is investigated in detail. No structural transition is present for these systems in this pressure range. RuC–Zinc blende is mechanically and dynamically unstable close to 100 GPa. RuC-Rhombohedral and Ru₃C-Hexagonal retain mechanical and dynamical stability up to 200 GPa. For all three systems the electronic bands and density of states spread out with pressure and the band gap increases with pressure for the semiconducting RuC–Zinc blende. From the computed IR spectrum of RuC–Zinc blende at 50 GPa it is noted that the IR frequency increases with pressure. Using a semi-empirical model for hardness it is estimated that hardness of all three systems consistently increases with pressure. The hardness of RuC–Zinc blende increases towards the superhard regime up to the limiting pressure of its mechanical stability while that of RuC-Rhombohedral becomes 30 GPa at the pressure of 150 GPa.     

Phase diagram of RDX (hexahydro-1,3,5-trinitro-s-triazine) at high pressures and temperatures

Abstract

The phase diagram of RDX-h₆ (hexahydro-1,3,5-trinito-s-triazine) and RDX-d₆ has been studied by Raman spectroscopy to more than 13 GPa at 295 K and 7.5 GPa between 150 and 450 K. Two stable high pressure phases have been found. γ-RDX or RDX-III forms from α-RDX above 3.8 GPa below 380 K. β-RDX forms when α- or γ-RDX are heated, can be retained metastably at low temperatues, and may be related to a very unstable form occasionally recovered at ambient pressure. Deuterium isotopic substitution and shear increase the temperature where β-RDX begins to form on heating.     

Structural,electronic and mechanical properties of alkaline earth metal oxides MO (M=Be,Mg, Ca,Sr, Ba)

The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.     

Phase diagrams in the proton conductor systems Sr6Ta2O11 × nH2O and Sr5.92Ta2.08O11.12 × nH2O

The systems Sr₆Ta₂O₁₁–H₂O and Sr_5.92Ta_2.08O_11.12–H₂O were investigated. At high temperatures, both compounds are normal proton conductors but at lower temperatures show the formation of hydrate phases (here labelled β-phases). The latter are deleterious if the above compounds were to be used in fuel cells, sensors and pumping devices. The phase diagrams of the 2 systems were determined using thermogravimetry. The solubilities of water vapor in the α-phases were measured. Considering 2-phase mixtures of α and β, the plateau vapor pressures were determined as well as the pertinent thermodynamic parameters. The α→α + β solvus was also investigated. The present study complements recent work [I. Animitsa, A. Nieman, A. Sharafutdinov, S. Nochrin, Solid State Ionics 136–137 (2000) 265; I. Animitsa, A. Nieman, S. Titova, N. Kochetova, E. Isaeva, A. Sharafutdinov, N. Timofeeva, Ph. Colomban, Solid State Ionics 156 (2003) 95].     

Addendum to “Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)” by K.-S. Lee et al. [J. Phys. Chem. Solids 73 (2012) 890]

While a paper mentioned above being published on line, we have become aware of the high-pressure neutron diffraction study of squaric acid (H₂C₄O₄) by C.L. Bull et al. They developed that neutron diffraction experiments could be performed under quasi-hydrostatic conditions to pressures of up to 18 GPa and showed that the tetragonal phase of H₂C₄O₄ was still observed at 14.5 GPa (above the critical pressure of P_c=0.75 GPa at room temperature) beyond the previous pressure limits of 7 GPa. Taking the high-pressure neutron diffraction results into consideration, modified temperature-pressure phase diagram in the paper stated above is reported.     

Pressure-induced phase transition in wurtzite ZnS: An ab initio constant pressure study

We study the pressure-induced phase transition of wurtzite ZnS using a constant pressure ab initio technique. A first-order phase transition into a rocksalt state at 30–35 GPa is observed in the constant pressure simulation. We also investigate the stability of wurtzite (WZ) and zinc-blende (ZB) phases from energy–volume calculations and Gibbs free energies at zero temperature and find that both structures show nearly similar equations of state and transform into a rocksalt structure around 14 GPa, in agreement with experiments. Additionally, we examine the influence of pressure on the electronic structure of the wurtzite and zinc-blende ZnS crystals and find that their band gap energies exhibit similar tendency and increase with increasing pressure. The calculated pressure coefficients and deformation potential are found to be comparable with experiments.     

Pressure-induced coordination crossover in magnetite; the breakdown of the Verwey–Mott localization hypothesis

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC), whereby charge density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse-spinel phase. The CC transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure the CC-transition temperature increases with pressure, reaching 300 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

High-pressure dielectric studies of a novel hydrogen-bonded ferroelectric (NH4)2H2P2O6

The hydrostatic pressure effect on the dielectric properties of (NH₄)₂H₂P₂O₆ ferroelectric crystal was studied for pressures from 0.1 MPa to 360 MPa and for temperatures from 100 to 190 K. The pressure–temperature phase diagram obtained is linear with increasing pressure. The paraelectric–ferroelectric phase transition temperature decreases with increasing pressure with the pressure coefficient dT_c/dp=?5.16×10^?2 K MPa^?1. Additionally, the pressure dependences of Curie–Weiss constants for the crystal in paraelectric (C₊) and ferroelectric (C_?) phases are evaluated and discussed. The possible mechanism of paraelectric–ferroelectric phase transition is also discussed.