Mössbauer studies of ɛ-Fe3−x Ni x N and γ′-Fe4−y Ni y N nanoparticles

Nanocrystalline ?-Fe_3?x Ni _x N (0.0?≤?×?≤?0.8) particles are synthesized by precursor technique and nitridation of decomposed products in NH₃ (g) in the temperature range 673 K-823 K. For x?=?0.1–0.4 compositions, single phase ?-Fe_3?x Ni _x N hexagonal structure with space group P6₃/mmc is formed, while for x?=?0.5–0.8, fcc γ′-Fe_4?y Ni _y N phase is also precipitated. The room temperature Mössbauer spectrum for all the compositions shows the presence of superparamagnetic doublet, which is attributed to ?-Fe_3?x Ni _x N phase. For x?=?0.5–0.8 compositions, two additional sextets are observed corresponding to two different iron sites, the corner position (Fe^c) and the fcc position (Fe^f), in γ′-Fe_4?y Ni _y N. The added Ni atoms preferentially substitute the corner Fe^c positions. The isomer shift, quadrupole splitting and hyperfine field values are found to change with the Ni content.     

Damage of Dusty Optical Elements in the Field of Continuous-Wave Laser Radiation

The structure and properties of high-pressure phases of iron nitrides Fe₇N₃ in the pressure range of 50–150 GPa have been studied with ab initio calculations within the electron density functional theory. A new phase Amm2-Fe₇N₃, which is the most energetically favorable in the pressure range of 43–128 GPa, has been found using the USPEX (Universal Structure Predictor: Evolutionary Xtallography) algorithms. It has been thermodynamically shown that another high-pressure phase β-Fe₇N₃ is isostructural to a similar phase of iron carbide. The elastic properties have been calculated for all modifications ε-, β-, and Amm2-Fe₇N₃ stable at high pressures.     

Perovskites Bi0.8La0.2FeO3 and Bi0.8La0.2Fe0.95Cr0.05O3: Crystal structure and magnetic and charge states of iron ions

Perovskites of the Bi_0.8La_0.2Fe_{1 ? x} Cr _x O₃ system (x = 0, 0.05) were investigated by Mössbauer spectroscopy in the temperature range of 298–800 K. The samples were fabricated by solid-state synthesis and had a rhombic structure. Iron ions in Bi_0.8La_0.2FeO₃ and Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ are situated in trivalent states. The magnetic transition temperatures (the Néel temperatures T _N ) T _N = 677.5 ± 2.5 K for Bi_0.8La_0.2FeO₃ and T _N = 647.6 ± 2.5 K for Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ are measured. The substitution of trivalent iron ions from trivalent chromium ions in the amount x = 0.05 in Bi_0.8La_0.2Fe_0.95Cr_0.05O₃ perovskite decreases the hyperfine magnetic field at nuclei ⁵⁷Fe in Fe⁺³-O-Cr⁺³ chains by 30 kOe.     

Superconductivity and magnetic order in RBa2Cu3Oz

Mössbauer studies of⁵⁷Fe in RBa_2?y K _y (Cu_1?x Fe _x )₃O_z, with R=Y and Pr;y=0 and 0.5;x=0.01, 0.05 and 0.1 andz between 5.9 and 7.1, have been performed. A minority of the iron ions enter the Cu(2) site and reveal its magnetic order. In nonsuperconducting YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.1 two distinctly inequivalent magnetic iron sites are observed, probably corresponding to iron in the Cu(2) site with different Ba?K neighbours. In superconducting (T _c =60 K) YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.5 one Cu(2) subsite remains magnetic (T _N=440 K). The implications of these findings on the valencies of the Cu ions are discussed.     

Structural and magnetic phase transitions occurring in Pr0.7Sr0.3MnO3 manganite at high pressures

The crystal and magnetic structures and the vibrational spectra of Pr_0.7Sr_0.3MnO₃ manganite are studied within the pressure range up to 25 GPa by methods of X-ray diffraction and Raman spectroscopy. Neutron diffraction studies have been performed at pressures up to 4.5 GPa. The magnetic phase transition from the ferromagnetic phase (T _C = 273 K) to the A-type antiferromagnetic phase (T _N = 153 K) is found at P ≈ 2 GPa. This transition is characterized by a broad pressure range corresponding to the phase separation. The Raman spectra of Pr_0.7Sr_0.3MnO₃ measured under high pressures significantly differ from the corresponding spectra of the isostructural doped A_{1 ? x} A′ _x MnO₃ manganites, (where A is a rare-earth ion and A′ is an alkaline-earth ion) with the smaller average ionic radius 〈r _A〉 of A and A′ cations. Namely, the former spectra do not include clearly pronounced stretching phonon modes. At P ～ 7 GPa, there appears the structural phase transition from the orthorhombic phase with the Pnma space group to the orthorhombic high-pressure phase with the Imma symmetry. In the vicinity of the phase transition, anomalies in the pressure dependences of the lattice parameters, unit cell volume, and phonon frequencies corresponding to the characteristic lattice vibration modes are observed.     

Equation of state and thermal expansivity of LiF and NaF

The high-pressure and high-temperature behaviors of LiF and NaF have been studied up to 37 GPa and 1000 K. No phase transformations have been observed for LiF up to the maximum pressure reached. The B1 to B2 transition of NaF at room temperature was observed at ～28 GPa, this transition pressure decreases with temperature. Unit-cell volumes of LiF and NaF B1 phase measured at various pressures and temperatures were fitted using a P–V–T Birch–Murnaghan equation of state. For LiF, the determined parameters are: α₀ = 1.05 (3)×10^?4 K^?1, dK/dT = ?0.025 (2) GPa/K, V ₀ = 65.7 (1) Å³, K ₀ = 73 (2) GPa, and K′ = 3.9 (2). For NaF, α₀ = 1.34 (4)×10^?4 K^?1, dK/dT = ?0.020 (1) GPa/K, V ₀ = 100.2 (2) Å³, K ₀ = 46 (1) GPa, and K′ = 4.5 (1).     

Metal-insulator transition in Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S crystals

Results of an experimental study of MnS, FeS, and Fe _x Mn_1?x S single crystals are presented. The phase composition, the lattice parameters, and the state of paramagnetic ions in Fe _x Mn_1?x S have been determined by x-ray diffraction analysis and Mössbauer spectroscopy. A sequence of transitions have been found in iron manganese sulfide with x = 0.29 at temperatures T ₁ ≈ 25–50 K, T ₂ ≈ 125 K, and T ₃ ≈ 190 K with a change in kinetic properties and the formation of a metallic state at low temperatures T ≈ 2 K. The possibility of a Mott-Hubbard transition in Fe _x Mn_1?x S sulfides with variation of the composition and the temperature is discussed.     

Thermodynamics of a Magnetic Transition in MnS<Subscript>2</Subscript> at High Pressures

The behavior of the specific heat of MnS₂ at high pressures has been studied. A significant increase in the transition temperature T_N to an antiferromagnetic state with the pressure from 48.2 K at atmospheric pressure to 76 K at a pressure of 5.3 GPa has been revealed. The initial pressure derivative is dT _N /dP = 4.83 K/GPa. It has been found that the parameter α = d(logT _N )/d(logV ) = ?6.6 ± 0.1 is significantly different from the value α = ?10/3 ≈ ?3.3 (Bloch relation), which is typical of numerous antiferromagnetic insulators—transition- metal oxides and fluorides. The volume jump at the magnetic transition point has been estimated. The necessity of direct dilatometric measurements of the volume has been justified.     

Neutron investigations of the magnetic properties of Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S under pressure up to 4.2 GPa

Fe _x Mn_1?x S belongs to the group of strong electron correlations compounds MnO. We present here experimental results for the antiferromagnetic iron–manganese sulfide system, based on X-ray and neutron diffraction studies. The neutron diffraction investigations were carried out at ambient conditions and at hydrostatic pressures up to 4.2 GPa in the temperature range from 65 to 300 K. Our results indicate that the Néel temperature of α-MnS increases up to room temperature by applying chemical (x _Fe) or weak hydrostatic pressure P. In Fe_0.27Mn_0.73S, the Néel temperature increases from 205(2) K (P = 0 GPa) to 280(2) K (P = 4.2 GPa) and the magnetization at 100 K decreases by a factor of 2.5 when the hydrostatic pressure increases from 0 to 4.2 GPa.     

Transition from the Kondo regime to long-range magnetic order in the FexV1−x S system

A study is reported on the electrical and magnetic characteristics of the Fe_xV_1?x S solid-solution system with x≤0.5. A maximum in the temperature dependence of resistivity ρ(T) characteristic of the Kondo effect has been observed for small x(x<0.01). For x>0.1, long-range magnetic order sets in in the system with T _K ≈ 100 K. Near x=0.05, the Fe²⁺ impurity behavior crosses over to a magnetically ordered phase. The electronic properties of Fe_xV_1?x S are typical of those of strongly correlated electronic systems. Both the electrical and magnetic data imply that carrier delocalization is the strongest at x=0.4.     

Terahertz Cyclotron Photoconductivity in a Highly Unbalanced Two-Dimensional Electron–Hole System

The magnetic properties of the α-Fe₂O₃ hematite at a high hydrostatic pressure have been studied by synchrotron Mössbauer spectroscopy (nuclear forward scattering (NFS)) on iron nuclei. Time-domain NFS spectra of hematite have been measured in a diamond anvil cell in the pressure range of 0–72 GPa and the temperature range of 36–300 K in order to study the magnetic properties at a phase transition near a critical pressure of ~50 GPa. In addition, Raman spectra at room temperature have been studied in the pressure range of 0–77 GPa. Neon has been used as a pressure-transmitting medium. The appearance of an intermediate electronic state has been revealed at a pressure of ~48 GPa. This state is probably related to the spin crossover in Fe³⁺ ions at their transition from the high-spin state (HS, S = 5/2) to a low-spin one (LS, S = 1/2). It has been found that the transient pressure range of the HS–LS crossover is extended from 48 to 55 GPa and is almost independent of the temperature. This surprising result differs fundamentally from other cases of the spin crossover in Fe³⁺ ions observed in other crystals based on iron oxides. The transition region of spin crossover appears because of thermal fluctuations between HS and LS states in the critical pressure range and is significantly narrowed at cooling because of the suppression of thermal excitations. The magnetic P–T phase diagram of α-Fe₂O₃ at high pressures and low temperatures in the spin crossover region has been constructed according to the results of measurements.     

Low temperature magnetic properties of Ti-rich Fe-Ti spinels

Low temperature hysteresis loops have been measured on compositions of the spinel series Fe_3-xTi_xO₄, 0?x?1, with x=0.4, 0.5, 0.6 and 0.8. All compounds studied exhibit an anomaly of the hysteresis parameters in the temperature range 40–80 K below which a marked effect of field cooling on the hysteresis loops is observed.     

Features of local crystallographic, magnetic, and valence states of iron ions in Bi1 − x Sr x FeO3 perovskites at x = 0–0.67

Perovskites of the Bi_{1 ? x} Sr _x FeO₃ system (x = 0–0.67) at T = 295 K and T > T _N are studied using the Mössbauer effect. When the strontium content x = 0.1–0.15, the structural transition from the rhombohedral to the cubic phase takes place. It is found that in samples of the Bi_{1 ? x} Sr _x FeO₃ system (x = 0.07–0.67), there are only two structurally nonequivalent states of iron ions that correspond to Fe³⁺ ions in octahedral and tetrahedral oxygen environments.     

Electrical resistivity and magnetic susceptibility studies of the system Mn5Si3-Fe5Si3

Electrical resistivity measurements have been performed on the system Mn_5?x,Fe_xSi₃ for the compounds x = 0,1,2,3,4 and 5 from 4.2 K to above room temperature. From the shape of the ρ(T) curves it can be inferred that the transition from antiferromagnetic to ferromagnetic ordering occurs in the concentration range 3 ? x ? 4; for Fe₅Si₃ and MnFe₄Si₃ the ρ(T) curves are characterized by a break in their slope, whereas for x = 1,2 and 3 a large minimum appears. Mn₅Si₃ exhibits two successive minima at 74 and 105 K. Magnetic susceptibility measurements for x = 1, 2 and 3 give confirmation of the Néel temperature for x = 1 and 2, whereas for x = 3 the behaviour is more complex.     

High pressure effect on the crystal and magnetic structure of Pr0.1Sr0.9MnO3 manganite

The crystal and magnetic structure of Pr_0.1Sr_0.9MnO₃ manganite has been studied by the neutron diffraction at high pressures up to 5 GPa in the temperature range 10?C295 K. At normal pressure and decreasing temperature the appearance of the C-type (T _N = 220 K) and G-type (T _N = 180 K) antiferromagnetic states occurs, which is accompanied by a structural phase transition from the cubic structure (Pm $ \bar 3 $ m space group) to the tetragonal structure (I4/mcm space group). It is shown that the temperature of the transition to the C-type antiferromagnetic phase increases with pressure with the pressure coefficient dT _N/dP = 4.0(5) K/GPa and the temperature of the transition to the G-type antiferromagnetic phase weakly depends on pressure.     

Effect of pressure and anionic substitution on the electrical properties of HgTeS crystals

The resistivity ρ and the Hall constant R for the HgTe_1?x S_x (0.04≤x≤0.6) crystals have been investigated in the temperature range 4.2–350 K in the magnetic fields B up to 14 T. The pressure dependences of the resistivity ρ have been measured at the pressures P as high as 1 GPa at temperature T=77–300 K and magnetic field B=0–2 T. It is found that the samples with x≤0.20 exhibit a decreasing dependence ρ(T) typical of zero-gap semiconductors, whereas the samples with x≥0.27 show the dependence ρ(T) characteristic of semimetals. For the semiconducting crystals with x≈0.20 and x≈0.14, the temperature coefficient of ρ(T) changes sign at T=265 and T>300 K, respectively. Under a pressure of ≈1 GPa, the temperature of the sign inversion decreases by ≈30 K. An increase in the magnetic field B and a rise in the temperature T lead to a change in the sign of the Hall constant R for the semiconducting samples, but do not affect the electronic sign of R for the semimetallic samples. The behavior of R and ρ correlates with the thermoemf data obtained at the quasi-hydro-static pressure P up to 3 GPa. It is demonstrated that the substitution of sulfur atoms for tellurium atoms brings about an increase in the concentration of electrons and a decrease in their mobility. The transition to the wide-gap semiconductor phase is observed at P>1–1.5 GPa. The conclusion is drawn that the semimetallic crystals HgTe_1?x S_x with x≥0.27 and HgSe are similar in properties.     

Mössbauer and magnetization studies of the U1−xNpxO2 fluorites

²³⁷Np Mössbauer effect and magnetic susceptibility measurements of the U_1?Np_xO₂ fluorite solid solution have been performed in the composition range 0.15 ? x ? 0.75. For x = 0.15 and 0.25, the Np ions order magnetically at a lower temperature T₀ than the bulk material (T_N) (T₀ ～ 19 K, T_N ～ 27 K for x = 0.15). For x = 0.50, T₀ ～ 10 K (T_N ～ 12 K from recent neutron diffraction measurements). For x = 0.75, T₀ ～ T_N ～ 9 K. The Np (induced) ordered moment is ～ 0.5 μ_B. The ²³⁷Np Mössbauer isomer shift shows that the Np ions are in a IV charge state.     

Possible oxygen hopping in the YBa2Cu3O7 system observed by Mössbauer spectroscopy

In situ high temperature⁵⁷Fe Mössbauer measurements have been performed on samples of YBa₂ (Cu_1?xFe_x)₃O_7?δ withx=0.005 andx=0.010, in pure oxygen or in air, in the range 295 K≤T≤640 K. TheT-dependence of Fe species, of the Debye-Waller factorf(T) as well as of the hyperfine parameters is analysed.     

Phase relations in the Fe-P system at high pressures and temperatures from ab initio computations

ABSTRACT

Based on the first-principles calculations within the density functional theory and crystal structure prediction algorithms iron phosphide phases stable under pressure of the Earth’s core and temperatures up to 4000?K were determined. A new low-temperature modification FeP-P2₁/c stable above ～75?GPa was predicted. Fe₂P with the allabogdanite structure has been established to be stable in the low-temperature region at ambient conditions. At 750?K it transforms into the barringerite structure. The transition from Fe₃P with schreibersite structure to Fe₃P-Cmcm was observed at 27?GPa, and the phase transition boundary is nearly isobaric. Fe₂P and FeP are thermodynamically stable at the Earth’s inner core pressures and 0?K according to the obtained results, whereas Fe₃P stabilizes with respect to decomposition to Fe?+?Fe₂P at high temperatures above ～3200?K.     

Structure and the electrical and magnetic properties of perovskite-like Gd x Cu3V4O12 oxide

A new perovskite-like compound Gd _x Cu₃V₄O₁₂ (x = 0.67?0.73) is synthesized under high pressures (P = 4?9 GPa) and at high temperatures (T = 1000°C). Its structure (space group Im3, Z = 2, a = 7.2930(5) ?) is estrablished by X-ray analysis. The bond lengths and bond angles are determined. The temperature dependences of electrical resistivity (10?C300 K) and magnetic susceptibility are studied. The high-pressure Gd _x Cu₃V₄O₁₂ phase is found to have a semi-conductor type of conductivity and paramagnetic properties.