Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.     

Morphology and magnetic properties of Fe x Co1−x /Co y Fe3−y O4 nanocomposites prepared by surfactants-assisted-hydrothermal process

Recently, we have demonstrated the successful synthesis of Fe _x Co_1−x /Co _y Fe_3−y O₄ nanocomposites with various alkaline solutions by using surfactants-assisted-hydrothermal (SAH) process. In this article, the synthesis of Fe _x Co_1−x /Co_yFe_3−y O₄ nanocomposites with their sizes varying between 20 nm and 2 μm was reported. X-ray powder diffraction (XRD) analyses showed that the surfactants, pH, precipitator, and temperature of the system play important roles in the nucleation and growth processes. The magnetic properties tested by vibrating sample magnetometer (VSM) at room temperature exhibit ferromagnetic behavior of the nanocomposites. These Fe _x Co_1−x /Co _y Fe_3−y O₄ nanocomposites may have a potential application as magnetic carriers for drug targeting because of their excellent soft-magnetic properties.     

Calculation of the electronic structure and hyperfine fields for Fe1 − x Co x B and (Fe1 − x Co x )2B compounds by the Korringa-Kohn-Rostoker method

The magnetic properties of Fe_{1 ? x} Co _x B and (Fe_{1 ? x} Co _x )₂B disordered compounds were investigated using first-principles calculations of the electronic structure in the framework of the density functional theory with the Korringa-Kohn-Rostoker method. The concentration dependences of the magnetic moments and the electron density were calculated for the Fe_{1 ? x} Co _x B solid solutions. The results obtained were used to analyze in detail and to interpret the transition from a magnetic phase to a nonmagnetic phase, which was previously revealed from the experiments in the compounds under investigation. The performed analysis of the calculated hyperfine fields induced by the electronic shells at the iron and cobalt atoms in the (Fe_{1 ? x} Co _x )₂B borides made it possible to explain the experimentally observed magnetic anisotropy.     

Characterization and magnetic properties of electrospun Co1−x Zn x Fe2O4 nanofibers

By the electrospinning and calcination techniques, we have prepared uniform nanofibers of Co_1−x Zn _x Fe₂O₄ (0.0≤x≤0.5) ferrites with diameters of 110–130 nm. The Co_1−x Zn _x Fe₂O₄ nanofibers are single-phase spinels and the lattice constant with Zn content deviates from the Vegard’s law for these Co_1−x Zn _x Fe₂O₄ nanofibers. The Co_1−x Zn _x Fe₂O₄ nanocrystal grains by which are built nanofibers increase with calcination temperature. Variations of coercivity and saturation magnetization with calcination temperature can be explained in terms of the grain-size (D) effect. The coercivity (H _c) of Co_0.5Zn_0.5Fe₂O₄ nanofibers varies as D ^0.65 and basically follows the predicted D ^2/3 dependence based on the random anisotropy model in a D range below the single-domain size around 40 nm. The saturation magnetization of Co_1−x Zn _x Fe₂O₄ nanofibers initially increases with increasing Zn content, reaches a maximum value at x=0.3 and then decreases with further increase of Zn content, while the coercivity exhibits a continuous reduction with the increase of Zn content.     

Electron spin resonance study of the dynamic magnetic susceptibility of CuO, Cu1−x Zn x O, and Cu1−x Li x O single crystals

Results are presented of studies of the dynamic magnetic susceptibility of CuO, Cu_1?x Zn _x O (x ≈ 1.5%), and Cu_1?x Li _x O (x ≈ 1%) single crystals. The orientational dependence of the ESR spectra was investigated at room temperature. The results for CuO are analyzed using a model of a quasi-one-dimensional antiferromagnet (S = 1/2) with anisotropic exchange interaction between Cu²⁺ spins in the chains and exchange coupling between the chains allowing for one-dimensional spin diffusion and spinon excitations. The estimated line width is of the same order of magnitude as the experimental data. Substituting Cu with Zn scarcely alters the spin dynamics of the Cu²⁺ ions, as in weakly diluted magnets. Lithium doping substantially increases the ESR line width and this is attributed to excess holes forming rapidly relaxing spin complexes with copper ions.     

Crystal structure and magnetic state of the LaMn1−x VxO3 perovskites

The crystal structure and the magnetic state of polycrystalline LaMn_1?x V_xO₃ (0.1<x<0.9) compounds have been studied by x-ray and neutron diffraction methods, as well as by magnetization and ac susceptibility measurements. It is shown that substitution of vanadium for manganese ions leaves the orthorhombic crystal structure of the compounds (space group Pnma) unchanged. The magnetic structure is observed to change from a canted antiferromagnetic ordering (wavevector k=[0, 0, 0], with the antiferromagnetic moments aligned with the a axis and the ferromagnetic component of the magnetic moment parallel to the b axis) at vanadium concentrations x<0.4 to a collinear antiferromagnetic ordering (with the magnetic moments parallel to the b axis) at x>0.8; at this transition occurs through an intermediate state exhibiting spin-glass properties.     

High-Pressure Synthesis of SeCu 1− x Zn x O 3 Perovskites

The SeCu 1 m x Zn x O 3 solid solution, with a distorted perovskite-type structure, has been synthesized under high pressures and temperatures. X-ray diffraction analysis indicates that the zinc ions occupy the copper sites, a solid solution being formed. It seems that high-pressure stabilises a small cation such as Se 4+ in the A site of the perovskite structure ABO 3 although the material is better described as formed by selenite anions \rm{SeO}_{3}^{-} and Cu 2+ /Zn 2+ cations.     

High-temperature background of internal friction in (Co45Fe45Zr10) x (Al2O3)100 − x , Co x (CaF2)100 − x , and Co x (PZT)100 − x nanocomposites

The elastic (G) and inelastic (Q ^?1) properties of (Co₄₅Fe₄₅Zr₁₀) _x (Al₂O₃)_{100 ? x} , Co _x (CaF₂)_{100 ? x} , and Co _x (PZT)_{100 ? x} (x = 23–76 at %) nanocomposites obtained by ion-beam sputtering are studied in the temperature range 300–900 K. A significant rise in the Q Q ^?1 (T) curve is observed at temperatures above 650 K, which is attributed to thermally activated migration of point defects under the conditions of confined geometry.     

Concentration-dependent crystal structure,elastic constants and electronic structure of Zr x Ti1−x alloys under high pressure

The physical properties of ZrxTi1-x（x=0.0, 0.33, 0.5, 0.67, 0.75 and 1.00） alloys were sinmlated by virtual crystal approximation （VCA） methods which is generally used for disordered solid solutions modeling. The elastic constant, electronic structure and thermal Equation of state （EOS） of disor- dered ZrxTi1-x alloys under pressure are investigated by plane-wave pseudo-potentia1 method. Our simulations reveal increasement of variations of the calculated equilibrium volumes and decrease- ment of Bulk modulus as a function of the alloy compositions. Lattice parameters a and c of alloys with differentZr concentrations decrease linearly with pressure increasing, but the c/avalues are increasing as pressure increases, indicating no phase transitions under pressure from 0 GPa to 100 GPa. The elastic constants and the Bulk modulus to the Shear modulus ratios （B/G） indicate good ductility of Zr, Zr0.33 Ti0.67 Zr0.5Ti0.5, Zr0.75Ti0.25 and Ti, but the Zr0.67Ti0.33 alloy is brittle under 0 K and 0 GPa. The metallic behavior of these alloys was also proved by analyzing partial and total DOS.     

X-ray, Mössbauer, and dielectric studies of the Co1 − x Ni x Cr2O4 ceramic system

The temperature dependences of the dielectric constant, ?(T), dielectric loss tangent, tanδ(T), and thermostimulated depolarization currents of (Co_{1 ? x} Ni _x )Cr₂O₄:y ⁵⁷Fe₂O₃ samples with 0.2 ≤ x ≤ 0.6 and 0.01 ≤ y ≤ 0.04 exhibit anomalies at temperatures of T ₁ ≈ 220 K and T ₂ ≈ 240 K that indicate a transition to an ordered ferroelectric state at temperatures below T ₂. Also observed at the same temperatures are abrupt changes in the isomer shift and quadrupole splitting for two Mössbauer spectral doublets of a sample with x = 0.2.     

Magnetic and electrical properties of weakly doped manganese-deficient La1 − x Ca x Mn1 − z O3 manganites

Samples of La_{1 ? x} Ca _x Mn_{1 ? z} O_{3 + δ} (x = 0.05?0.15) with deficient manganese and excess oxygen δ do not pass into a metallic state and have low spin ordering temperatures T _C at acceptor Mn⁴⁺ concentrations near the percolation threshold. These results are explained by carrier localization in clusters near cation vacancies. A break in the carrier transport chain Mn-O-Mn in the form of absent manganese favors cluster formation and decreases the double exchange energy and T _C of the samples. Closeness to the percolation threshold results in strong (more than four orders of magnitude) changes in the electrical resistivity in a magnetic field. The changes in the cluster sizes with the temperature and the magnetic field that are determined from the magnetotransport properties are satisfactorily described in the model of phase separation into small-radius metallic droplets in a dielectric paramagnetic and an antiferromagnetic matrices.     

High temperature electrical properties and defect structure of Co1−xMgxO

The electrical conductivity and thermoelectric power of Co_1−xMg_xO solid solutions with x ⩽ 0.85 were investigated in the range 700–1100°C and for oxygen partial pressures in the range 1–10⁻¹⁶ atm. The experimental results show that an ideal point defect model of isolated cobalt vacancies cannot explain nonstoichiometry of Co_1−xMg_xO materials with x, at least, less than 0.3. Furthermore, the hole mobility in Co_1−xMg_xO with x < 0.6 was found to be nonactivated suggesting that holes in these materials are itinerant carriers. For x > 0.6, the mobility is thermally activated indicating a change to small polaron conduction. The experimental evidence for complex defect structure and bandlike conduction in CoO is in agreement with the conclusions of recent theoretical studies of 3-D transition metal monoxides.     

EPR observations of anomalous triplet states in Ba1−x KxBiO3 and BaPbyBi1− y O3

Electron paramagnetic resonance (EPR) spectra of samples of the systems Ba_1−x K_xBiO₃ and BaPb_yBi_1−y O₃ are investigated over wide ranges of composition and temperature. Two main lines in the EPR spectrum with factors g ₁≈2.1 and g ₂≈4.2 are found for all compositions. It is shown that the observed EPR line with g ₂≈4.2 is due to oxygen ions. This probably indicates the presence of oxygen ions with different effective charges, i.e., the existence of charge density waves in the oxygen-ion sublattice in addition to charge density waves in the bismuth sublattice. Zh. éksp. Teor. Fiz. 115, 1326–1336 (April 1999)     

Theory of the electronic structure of Ga1-yInyNxAs1−x and related alloys

Abstract

We present a quantitative k.P Hamiltonian which describes analytically the composition dependence of the energy gap, interband momentum matrix element, band edge effective masses and conduction band dispersion of GaN_XAs_1?x alloys for low N concentrations (x < ～ 0.05). The model has been confirmed using an sp³s? tight-binding Hamiltonian whose results agree well both with experiment and with previous pseudopotential calculations. The model should be of wide use to guide the future development of this material system and its applications.     

Neutron diffraction study of the oxide conducting δ1-phase of (Bi2O3)1−x(Y2O3)x (x=0.25)

The atomic parameters of the average cell of δ¹-Bi(Y)O_1.5 were determined by powder neutron diffraction. The evidence indicates that the disorder in the structure has many features in common with the structure of the oxygen deficient zirconia. Most oxygens (78%) are in sites displaced 0.335 Å along 〈100〉 directions from the normal fluorite positions, while a smaller proportion (22%) are displaced 0.80 Å along 〈111〉 directions and no oxygen remains in normal positions. In addition to the anion displacements a smaller displacement (0.25 Å) along the 〈111〉 direction was found for the cations. Comparison with the structure of β-Bi₂O₃ suggests that the displacements may be precursors to a δ→β phase transition.     

Spin-wave resonance in [Co x Ni1 − x ]N and [Co x P1 − x ]N gradient films

Gradient films of ferromagnetic 3d metals with prescribed magnetic potential profile along the film thickness are obtained. It is found that the spin-wave resonance spectrum in these films is characterized by anomalous dependences of resonance fields of spin-wave modes H _r on the mode number: H _r(n) ～ n, H _r(n) ～ n ^2/3.     

Crystal structure and photoluminescence of (Ba1−x−ySryEux)9Sc2Si6O24

Divalent europium-doped alkaline earth metal silicate phosphors, (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (x=0.005–0.1, y=0–0.95), have been successfully prepared by solid-state reaction at 1350 °C. The analysis of X-ray diffraction shows that the compounds are in a single phase at the proper concentration of Sr²⁺. At room temperature, the Eu²⁺-activated Ba₉Sc₂Si₆O₂₄ phosphor exhibits a single emission band peaking at about 506 nm. With the increasing content of Sr²⁺, the luminescent intensity of (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ weakens, and the emission peak shifts towards red. Luminescence concentration quenching occurs when Eu²⁺ content x is more than 1 mol% in (Ba_1?x?ySr_yEu_x)₉Sc₂Si₆O₂₄ (y=0/0.2). At low temperatures (Ba_0.9?ySr_yEu_0.1)₉Sc₂Si₆O₂₄ (y=0/0.2) phosphors have two emission bands corresponding to different Eu²⁺ crystallographic sites. The high energy peak (P₁) is quenched at room temperature, while the low energy peak (P₂) weakens much more slowly owing to the energy transfer from P₁ to P₂.     

Synthesis and electrochemical properties of Li8 − x Zr1 − x Nb x O6 solid solutions

New lithium-conducting solid solutions based on lithium orthozirconate have been synthesized by mutual doping of the related structures Li₈ZrO₆ and Li₇NbO₆. The main factor determining the increase in the electrical conductivity of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ solid solutions is the formation of lithium vacancies in the tetrahedral and octahedral layers. The practical stability of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ ceramics to metallic lithium has been studied.