Phase diagrams of the CoMnO system in air

A retrospective critical analysis of phase diagrams of the CoMnO system in air has been made. A high-temperature phase equilibrium of the CoMnO system in air and phase diagrams of this system under different cooling conditions (quenching in water, quenching in air, cooling at rate of 25°K h^?1) have been constructed. A comparative analysis of these diagrams shows that whatever the cooling rate, cooling does not preserve the high-temperature state of the system and is accompanied (depending on cooling conditions, temperature and Co/Mn ratio) by one or more of the following phenomena: (1) oxidation of the Co_NMn_1?NO solution to spinel-type solid solutions (2) merging of a cubic and tetragonal spinel phase and formation of a homogeneous tetragonally distorted spinel (3) tetragonal distortion of the spinel lattice (4) decomposition of the cubic spinel into a cubic and tetragonal spinel. (5) decomposition of the cubic spinel into a cubic, tetragonal and slightly distorted tetragonal spinel. Therefore, the form of the phase diagram of the CoMnO system in air is entirely determined by the method of cooling.     

Temperature evolution of the crystal structure of Bi1 − x Pr x FeO3 solid solutions

The crystal structure of solid solutions in the Bi_{1 ? x} Pr _x FeO₃ system near the structural transition between the rhombohedral and orthorhombic phases (0.125 ≤ x ≤ 0.15) has been studied. The structural phase transitions induced by changes in the concentration of praseodymium ions and in the temperature have been investigated using X-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. It has been established that the sequence of phase transformations in the crystal structure of Bi_{1 ? x} Pr _x FeO₃ solid solutions with variations in the temperature differs significantly from the evolution of the crystal structure of the BiFeO₃ compounds with the substitution of other rare-earth elements for bismuth ions. The regions of the existence of the single-phase structural state and regions of the coexistence of the structural phases have been determined in the investigation of the crystal structure of the Bi_{1 ? x} Pr _x FeO₃ solid solutions. A three-phase structural state has been revealed for the solid solution with x = 0.125 at temperatures near 400°C. The specific features of the structural phase transitions of the compounds in the vicinity of the morphotropic phase boundary have been determined by analyzing the obtained results. It has been found that the solid solutions based on bismuth ferrite demonstrate a significant improvement in their physical properties.     

Preparation and characterization of manganese and cobalt based semiconducting ceramics

The spinel phases Mn_3-x Co _x O₄ are prepared directly and at low temperature (600-700°C) by means of thermal decomposition of mixed oxalate salt precursors in air or controlled atmosphere. The powders so obtained when sintered at 1200°C behave as semiconducting or insulating ceramics, depending on their cobalt content. The electrical properties of these ceramics have been found to be related to the distribution and valencies of the cations in the spinel structure. The study of their crystalline structure and stability, complemented by electrical measurements have permitted us to distinguish two types of compounds. The first type includes those given by Mn_3-x Co _x O₄ with 0 < x < 1. These are stable at high temperature, have a tetragonal structure and are insulators. The cation distributions for them can be deduced from that of hausmannite as given by Mn²⁺ [Mn³⁺ ₂]O₄, by substituting Mn²⁺ ions with Co²⁺ ions. The second type of compounds correspond to the cubic phases and occur for 1 < x < 3. These are unstable at high temperature and show a lower resistivity (e.g. 360 ° cm) which is of particular interest for their application in the design of negative temperature coefficient (N.T.C.) thermistor components.     

On the phase diagram of the [(CH3)4N]2ZnCl4−xBrx system

The [(CH₃)₄N]₂ZnCl_4?xBr_x system shows a complete miscibility with a common Pnma high temperature phase. The (x,T)-phase diagram (x given by [(CH₃)₄N]₂ZnCl_4?xBr_x) was determined by means of DSC- and X-ray measurements. In the vicinity of both end members an analogy to the (P,T)-phase diagrams of pure compounds is observed with an increasing x corresponding to an increase of pressure. In the intermediate part of the system other effects become important leading to large coexistence regions of different phases. This is evidently due to the simultaneous occupancy of anion tetrahedra by different numbers of Cl and Br atoms. The non-equivalent ZnX₄-tetrahedra of solid solutions do not suppress the occurence of the incommensurate phases. They exist between x = 0 to ?3 and are interrupted by a supposedly ferroelectric phase occuring up to x ?0.4. Around x ? 3 a triple point occurs the nature of which needs a closer elucidation.     

Phase diagram of Fe(1−x)CoxCl2; a random mixture of two antiferromagnets with competing spin anisotropies

Concentration vs transition temperature phase diagram of a random mixture of two anisotropic antiferromagnets, FeCl₂ and CoCl₂, is obtained from the measurement of the susceptibility on the single crystals. Two distinct critical points, one along the c-axis and the other in the c-plane, are observed for the respective concentrations between x = 0.264 and x = 0.481. Three kinds of ordered phases, namely, Fe-rich and Co-rich antiferromagnetic phases and a new phase are found. The phase diagram shows a tetracritical point as well.A hump is observed in the temperature dependence of the susceptibility along the c-axis (c-plane for x ? 0.3) near the ordering temperature occuring in the c-plane (c-axis for x ? 0.3).     

Magnetic resonance in a gallium-doped Cu–Cr–S structure

A layered Cu–Cr–S structure doped with Ga ions and consisting of single-crystal CuCrS₂ layers, embedded with thin plates of spinel phases CuCr₂S₄ and CuGa_xCr_2–xS₄, has been studied using the magnetic resonance and magnetic susceptibility methods. The Curie temperature and the saturation magnetization of the spinel phases of the samples have been determined. The spinel phase layer thickness has been estimated.     

Epr study of CoxZn1−xRh2O4 spinel solid solution

The EPR powder spectra of Co_xZn_1?xRh₂O₄ spinel solid solutions have been studied in the temperature range, 6–300 K for x ? 0.10. The principal features of the spectrum have been examined as a function of the temperature and of the composition. Evidence is presented that the solid solutions are antiferromagnetically ordered for x ? 0.40.     

The structural and magnetic properties of Ni2Mn1−xBxGa Heusler alloys

The influence of the substitution of manganese by boron on the crystal structure and magnetic properties of Ni₂Mn_1−xB_xGa Heusler alloys with 0?x?0.5 has been investigated using X-ray diffraction, thermal expansion, resistivity, and magnetization measurements. The samples with concentrations x<0.25 were found to be of single phase and belonged to the cubic L2₁ crystal structure at room temperature. Crystal cell parameters of the alloys decreased from 5.830 to 5.825 Å with increasing boron concentration (x) from 0 to 0.25. The alloys were ferromagnetically ordered at 5 K and the saturation magnetization decreased with increasing boron concentration. The ferromagnetic ordering and structural transition temperatures for 0?x?0.3 have been observed and the phase (x−T) diagram of the Ni₂Mn_1−xB_xGa system was constructed. The phase (x−T) diagram indicates that the ground state of Ni₂Mn_1−xB_xGa alloys belongs to ferromagnetic martensitic, premartensitic, and austenitic phases in x?0.12, 0.12<x?0.18, and 0.18<x?0.3, respectively. The relative influence of cell parameters and electron concentrations on the phase diagram is discussed.     

Magnetic and piezoelectric properties of the Bi1 − x La x FeO3 system near the transition from the polar to antipolar phase

The crystal structure, piezoelectric and magnetic properties of the Bi_{1 ? x} La _x FeO₃ solid-solution system near the structural transition between the rhombohedral and orthorhombic phases (0.15 ≤ x ≤ 0.2) have been investigated. The regions of existence of the polar rhombohedral and orthorhombic phases have been determined, and the sequence of structural transitions as a function of the lanthanum ion concentration and temperature has been studied. The maximum piezoelectric signal is found for the solid solution with the composition x = 0.16, which has a single-phase rhombohedral structure. The relation between the type of crystal structure distortions and the increase in the magnetization upon the concentration-driven structural transition from the polar to antipolar phase has been established.     

Dielectric studies of phase transitions in the ferroelectric CdTiO3 and the Sr1−x CdxTiO3 solid solution

Temperature dependences of the permittivity and of the dielectric hysteresis loops in ceramic samples of nominally pure CdTiO₃ and a Sr_1?x Cd_xTiO₃ solid solution were studied. At 76.5±0.5 K, CdTiO₃ was established to undergo a ferroelectric phase transition close to the tricritical point. The temperature dependence of spontaneous polarization of CdTiO₃ is described within the Landau theory of phase transitions with the critical order parameter exponent ≈0.25. The phase diagram of the Sr_1?x Cd_xTiO₃ solid solution was drawn in (T, x) coordinates, and the critical concentration x _c =0.002, above which an induced polar state sets in the solid solution, was determined.     

New ferrimagnetic spinel compositions in the system MCr2S4−xSex where M=Fe,Co, Mn

Phase relationship between ferrimagnetic semiconducting spinels of the type MCr₂S₄ and defect NiAs compositions of the type MCr₂Se₄ (where M=Mn, Fe, Co) are established. It was found that the amount of Se which can be substituted, with retention of the spinel structure, decreases from MnCr₂S_4?xSe_x (x=0 to x=2) to FeCr₂S_4?xSe_x (x=0 to x=1·25) to CoCr₂S_4?xSe_x (x=0 to x=1). This phenomena is accounted for on the basis of sulfide spinel stability and unit cell size. The Curie temperatures of the spinel compositions decrease slowly with increasing Se content. This is presumably caused by weakening of the spinel A-B superexchange interaction.     

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.     

Magnetotransport and magnetic properties of sulfospinels Zn x Fe1−x Cr2S4

Cr-based chalcogenide spinels, which do not have heterovalency and distortion-induced ions such as manganese oxides with perovskite structure, have demonstrated the existence of colossal magnetoresistance. In order to investigate the magnetotransport phenomena and magnetic properties of sulfospinels Zn _x Fe_1?x Cr₂S₄, polycrystalline Zn _x Fe_1?x Cr₂S₄ samples were synthesized in the 0?≤?x?≤?0.2 range by a solid reaction method. The crystal structure for x?=?0.05, 0.1, and 0.2 turned out to be cubic at room temperature by X-ray diffraction measurement. In magnetoresistance measurement, Zn _x Fe_1?x Cr₂S₄ samples indicate that this system is semiconducting below about 150 K. The temperature of maximum magnetoresistance is almost consistent with Curie temperature. The isomer shift and the electric quadrupole shift of Zn _x Fe_1?x Cr₂S₄ samples by Mössbauer experiment show that Fe²⁺ ions occupy the tetrahedral site in the spinel structure. As the Zn ions are substituted for Fe ions, the Jahn–Teller relaxation slows down and the electric quadrupole shift increases. The magnetotransport phenomena of Zn _x Fe_1?x Cr₂S₄ is related to Jahn–Teller effect and half-metallic electronic structure, which are different from the double exchange interactions of the manganite La–Ca–Mn–O system or the triple exchange interactions of sulfospinel Cu _x Fe_1?x Cr₂S₄.     

Dielectric investigations of solid solutions SrTiO3-KTaO3 and SrTiO3-KNbO3

The temperature dependences of the dielectric constant and dielectric hysteresis loops in ceramic samples of (1 ? x)SrTiO_3?x KNbO₃ and (1 ? x)SrTiO_3?x KTaO₃ (0 ≤ x ≤ 0.3) solid solutions prepared using different heat treatments have been investigated. Phase diagrams of the studied solid solutions have been constructed in the T-x coordinates. It has been shown that, after quenching of samples (spontaneous cooling at room temperature after long-term heating at the sintering temperature of the ceramic samples), the temperature of the induced phase transition increases because of the weakening of random electric fields associated with nonisovalent impurities due to their “frozen” nonequilibrium redistribution. For small concentrations x, strong dielectric relaxation is observed in the temperature range of 150–250 K. A model of relaxing centers, which is based on the local charge compensation of heterovalent impurities, has been proposed.     

XRD and XPS characterization of mixed valence Mn3O4 hausmannite thin films prepared by chemical spray pyrolysis technique

Spray pyrolysis technique has been employed successfully for the synthesis of single phase mixed valence spinel hausmannite (Mn₃O₄) thin films using alcoholic start solution of manganese acetate (Mn(CH₃COO)₂·4H₂O) on pyrex glass substrates at atmospheric pressure using air as a carrier gas. Thermal decomposition of the precursor in the temperature range 320-490 °C led to the formation of Mn₃O₄ phase as revealed from the thermogravimetry analysis. Prepared samples are characterized by X-ray diffraction that shows spinel structure with space group I4₁/amd. Pure and well crystallized specimen is subjected to X-ray photoelectron spectroscopy for the surface chemistry investigation of these systems at a molecular level. Surface Mn/O ratio is compared to the bulk composition of the sample. Atomic force micrographs revealed that the morphology and the surface grains of the films largely influenced by the substrate temperature.     

Magnetic,electrical and structural properties of some ternary and quaternary spinels with chromium

Spinel compounds with the general formulas ACr₂X₄ and ACr_2−xB_xX₄ (where A=Cd, Zn, Hg, Ga, Cu; X=S, Se, Te, O; B=Ga, In, Sb), including also substitution of two different cations in the tetrahedral subarray, exhibit different correlations of the magnetic and electrical properties. These properties are correlated with the ionic radii of cations and anions. The solid solutions of the boundary compounds reveal, e.g. correlations of metallic conductivity and a semiconductor–metal phase transition. In some spinel solid solutions the latter phase transition is accompanied by the magnetic phase transitions, i.e. either AF-F or Fi-F. Magnetic and electrical properties and their correlations in different spinel series with chromium are discussed in the frames of the phase diagram of the spinel-type compounds with chromium. Different mechanisms leading to the spin-glass state are discussed and illustrated.     

自旋玻璃的重入行为及CoxZn1-x(FeyCr1-y)2O4尖晶石系统的磁相图

本文研究了Co_xZn_1-x(Fe_yCr_1-x2O₄尖晶石系统的磁性,测量了不同成份样品的低频弱场交流磁化率与低场直流磁化强度的温度关系。根据实验结果,给出了该系统可能的磁相图。发现在该系统中相当宽的成份范围内,都存在自旋玻璃的重入现象。同时发现,自旋玻璃的重入温度随磁性离子浓度增加而增加。这些行为是磁性离子浓度含量较高和多种磁性离子共存系统的共同特性。还讨论了自旋玻璃重入行为 关键词：     

Description of ferroelectric phase transitions in solid solutions of relaxors in the framework of the random-field theory

A model based on the random-field theory is proposed for calculating the properties of solid solutions of ferroelectric relaxors. The electric dipoles randomly distributed in the system are treated as sources of random fields. The random field distribution function is calculated taking into account the contribution of nonlinear and correlation effects and the differences in the dipole orientations for different solid solution components. The dependence of the phase transition temperature T _c on the concentration of solid solution components is analyzed. Numerical calculations are performed for the lead scandoniobate and lead scandotantalate solid solutions (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x with different degrees of ordering and the lead magnoniobate and lead titanate solid solution (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃)_x. It is shown that the higher transition temperature for more disordered solid solutions of the composition (PbSc_1/2Nb_1/2O₃)_1?x (PbSc_1/2Ta_1/2O₃)_x in the range 0≤x<0.5 is associated with the larger nonlinearity coefficient for PbSc_1/2Nb_1/2O₃ as compared to that for PbSc_1/2Ta_1/2O₃. The theory provides a means for calculating the region of the coexistence of the phases with different symmetry groups in the temperature-composition phase diagram of the (PbMg_1/3Nb_2/3O₃)_1?x (PbTiO₃) solid solution. Numerical calculations with the use of the fitting parameters obtained from the known transition temperatures T _c for the solid solution components adequately describe the experimental phase diagrams for the aforementioned solid solutions of ferroelectric relaxors.     

Investigation of the magnetic properties of homogeneous copper-manganese alloys

The magnetic characteristics of homogeneous copper—manganese alloys Cu_{1 ? x} Mn _x are studied by the muon spin relaxation technique for the first time. It is revealed that the specific magnetic phase, which is most likely characterized by a fast spin dynamics and the absence of long-range order, is formed in alloys with concentrations 0.2 < x < 0.7 in the temperature range 10–330 K. The complete magnetic phase diagram is constructed.     

Heat capacity and thermal conductivity of Fe x Mn1 − x S single crystals

This paper reports on the results of investigations of the thermal properties and thermal conductivity of single crystals of homogeneous solid solutions Fe _x Mn_{1 ? x} S with a cubic NaCl structure, which have been prepared by the cation substitution for divalent manganese ions in manganese monosulfide. It has been revealed that the heat capacity and thermal conductivity exhibit anomalies in the range of the magnetic transition. The cation substitution is accompanied by an increase in the phase transition temperature.