Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.     

Positive magnetoresistance effect in rare earth cobaltites

The structure, magnetic, and magnetotransport properties of the Pr_0.5Sr_0.5Co_{1 ? x} Fe _x O₃ system have been studied. The ferromagnet-spin glass (x = 0.5)-G-type antiferromagnet (x = 0.7) transitions and the metal—insulator transitions (x = 0.25) have been revealed. It has been established that the magnetoresistance of the metallic ferromagnetic cobaltites changes sign from positive to negative as the external magnetic field increases. The positive component increases and the negative component decreases with decreasing temperature. The negative magnetoresistance increases sharply in the insulating spinglass phase. Possible causes of the low-magnetic-field positive magnetoresistance in the rare earth metallic cobaltites are discussed.     

Thermal conductivity and magnetic properties of the B substituted Ca3Co4O9

In this study, we reported the effects of the boron (B) substitution into the Ca site in the Ca₃Co₄O₉ system on the electrical, thermal and magnetic properties between 300 K and 5 K. The results indicated that the B-substitution into the system caused an increase of resistivity due to the decrease on carrier concentration. Thermal conductivity decreased for the x = 0.5 B-substituted sample and then increased with increasing the B-content. Analysis on the thermal conductivity of samples showed that the phonon–phonon interaction term is the dominant component in the total thermal conductivity for all the samples. It was found that the point defect contribution to the thermal conductivity increased by increasing the B-content. The temperature dependence of magnetic susceptibility showed a paramagnetic behavior at room temperature and ferrimagnetic behavior below 20 K for unsubstituted sample. But, the magnetization decreased in the B-substituted samples. The substitution of B into the Ca site destroyed the interlayer coupling, which resulted in the decrease of the ferromagnetic behavior. The susceptibility data was fitted using Curie–Weiss law with temperature independent term and the μ_eff values were calculated to be 1.42 μ_B and 3.89 μ_B for unsubstituted sample and the highest B-substitution, respectively.     

Anomalies of the electronic structure and physical properties of rare-earth cobaltites near spin crossover

The features of the characteristics of LnCoO₃ cobaltites, where Ln is a rare-earth element, are discussed. Both experiment and theory demonstrate that their essentials are related to the low-spin ground state of cobalt ions. The thermally induced occupation of the excited high-spin state gives rise to peaks in the magnetic susceptibility, specific heat, and thermal expansion, as well as to a smooth insulator–metal transition. The analysis is based both on the data from the current literature concerning LaCoO₃ and in many aspects on our own studies of GdCoO₃ and La_1?x Gd _x CoO₃ solid solutions.     

Magnetic and electrical properties of intercalated phases in the (Cr, Cu)-HfSe2 system

It has been shown that intercalation of the HfSe₂ compound with chromium atoms results in an increase in the magnetic susceptibility and a decrease in the resistivity while retaining the semiconductor conductivity type. The Cr _x HfSe₂ compounds exhibit a paramagnetic behavior at temperatures above 2 K in the entire concentration range 0 ≤ x ≤ 0.25. It has been revealed that an increase in the electron density due to additional introduction of copper can cause the appearance of a cluster-spin-glass-type state in Cr _x Cu _y HfSe₂ compounds. The data obtained indicate a large role of the indirect exchange interaction via conduction electrons in the formation of the magnetic state in layered intercalated compounds based on transition metal dichalcogenides.     

Low-temperature magnetic ordering in the perovskites Pr1−xAxCoO3 (A=Ca,Sr)

The magnetic and electrical properties of polycrystalline Pr_1?xA_xCoO₃ cobaltites with A=Ca, Sr and 0≤x≤0.5 were studied in the temperature range 4 K≤T≤1000 K and field up to 7 T. The X-ray analyses show the presence of only one phase having monoclinic or orthorhombic symmetry. The magnetic measurements indicate that the Ca-doped samples have at low temperatures, similar properties to the frustrated magnetic materials. PrCoO₃ is a paramagnetic insulator in the range from 4 to 1000 K. The Sr-doped cobaltites exhibit two phase transitions: a paramagnetic–ferromagnetic (or magnetic phase separated state) phase transition at about 240 K and a second one at about 100 K. The magnetic measurements suggest the presence of magnetic clusters and a change in the nature of magnetic coupling between Co ions at low temperatures. A semiconducting type behavior and high negative magnetoresistance was found for the Ca-doped samples, while the Sr-doped ones were metallic and with negligible magnetoresistance. The results are analyzed in the frame of a phase separation scenario in the presence of the spin-state transitions of Co ions.     

Effect of homovalent (I−Br−) ion substitution on the ionic conductivity of LiI1−x Brx systems

The study of electric conductivity in the whole range of compositions of mixed LiI_1?x Br_x crystals has shown that doping of pure lithium halide (LiI or LiBr) by homovalent substitution leads to an increase in conductivity. This enhancement is essentially pronounced in the solid solution domains near the compositions of pure compounds (x < 0.15 and x > 0.90). Maximum conductivity is attained for the two phase composition LiI_0.75Br_0.25 (5 × 10^?7 S cm^?1 at 293 K) compared to those of starting compounds (4 × 10^?8: LiI and 9 × 10^?9: LiBr at 293 K). An Arrhenius behaviour of the conductivity evolution versus the inverse of the temperature shows that variations in conductivity are related to those of the activation energy whose minimum is close to 8.7 Kcal mole^?1. Lattice strain involved by substituting anions of different raddi could be the factor which increase the defect population.     

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.     

Correlation between the magnetic and electrical properties of the (VS)x(Fe2O3)2−x oxysulfide system

The correlation between the magnetic and electrical properties of the (VS)_x(Fe₂O₃)_2?x (0.9<x<1.25) oxysulfide solid solutions has been studied. The crossover of conductivity from the semimetallic to semiconducting type is accompanied by changes in the magnetic susceptibility, which are characteristic of the transition from delocalized to localized electrons. For x=1.25, a region of the ferromagnetic ordering has been established in the temperature range 90–120 K.     

The magnetic susceptibility of hydrogen-doped partially crystalline (Zr76Ni24)1−xHx metallic glasses

The magnetizations of Zr₇₆Ni₂₄ metallic glass and hydrogen-doped partially crystalline (Zr₇₆Ni₂₄)_1−xH_x metallic glasses have been measured in the temperature range 10-300 K and magnetic fields up to 2 T for various dopant concentrations (x=0, 0.024, 0.043, 0.054). It is found that the samples are paramagnetic and magnetic susceptibility at room temperature, χ(300 K), shows a nonmonotonic behaviour upon hydrogenation. The values of χ(300 K) of the hydrogen-doped partially crystalline (Zr₇₆Ni₂₄)_1−xH_x metallic glasses are reduced with increase in hydrogen content up to x=0.043, whereas for x=0.054, an enhancement of χ(300 K) has been revealed. The magnetic susceptibility is weakly temperature dependent down to 110 K, below which an increase is observed. A shallow minimum exists between 90 and 120 K. The form and magnitude of the observed temperature dependence of the magnetic susceptibility are well accounted for by the sum of the quantum corrections to the magnetic susceptibility. Hydrogen reduces the electronic diffusion constant and influences strongly the quantum interference at defects, slowing down the spin diffusion and enhancing the magnetic susceptibility in the temperature range from 110 down to 10 K.     

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.     

A semimetal model of the normal state magnetic susceptibility and transport properties of Ba(Fe1−xCox)2As2

A simple two-band 3D model of a semimetal is constructed to determine which normal state features of the Ba(Fe_1?xCo_x)₂As₂ superconductors can be qualitatively understood within this framework. The model is able to account in a semiquantitative fashion for the measured magnetic susceptibility, Hall, and Seebeck data, and the low temperature Sommerfeld coefficient for 0 < x < 0.3 with only three parameters for all x. The purpose of the model is not to fit the data but to provide a simple starting point for thinking about the physics of these interesting materials. Although many of the static magnetic properties, such as the increase of the magnetic susceptibility with temperature, are reproduced by the model, none of the spin-fluctuation dynamics are addressed. A general conclusion from the model is that the magnetic susceptibility of most semimetals should increase with temperatures.     

The effects of counter cation on lithium ion conductivity: In the case of the perovskite-type titanium oxides of La2/3 − x Li3xTiO3 and LaTiO3

We performed hybrid-DFT calculations for La_2/3 ? xLi_3xTiO₃ (LLT) with lithium ion conductivity, in order to investigate the detailed lithium ion conductive mechanism from the viewpoint of molecular orbital (MO) method. It was concluded that the very ionic lithium ion in bottleneck accelerates the lithium ion conduction. The calculated MO shows no chemical bonding between lithium ion and other ions. In comparison with the perovskite-type trivalent titanium oxide of LaTiO₃, the effect of the titanium's reduction was also investigated. We showed the possibility of the high lithium conductivity in LaTiO₃.     

Magnetic and dielectric properties of nanophase manganese-substituted lithium ferrite

Nanocrystalline manganese-substituted lithium ferrites viz. Li_0.5Fe_2.5−xMn_xO₄ (2.5≤x≥0) were prepared by sol-gel autocombustion method. X-ray diffraction analysis confirmed that as the concentration of manganese increases the cubic phase changes to the tetragonal phase. The variation of saturation magnetization was studied as a function of manganese content. All the compositions indicate that they are ferrimagnetic in nature. The dielectric constant, dielectric loss tangent and ac conductivity of all samples were measured at room temperature as a function of frequency. These parameters decrease with increase in frequency for all of the samples. The substitution of manganese plays an important role in changing the structural and magnetic properties of these ferrites. The compositional variation of dielectric constant and d.c. resistivity shows an inverse trend of variation with each other.     

Study of DC conductivity and relative magnetic permeability of nanoparticle NiZnFe2O4/PPy composites

The DC conductivity and the relative magnetic permeability have been measured as functions of temperature for five powder samples of nanoparticle ferrites (Ni_xZn_1−xFe₂O₄; x=0, 0.25, 0.5, 0.75 and 1), a pure polypyrrole (PPy) powder sample and many composite samples prepared by mixing different ratios of the ferrites to PPy. By comparing the results it is found that there is an obvious increase in DC conductivity of the ferrite/PPy composite samples compared to the corresponding pure ferrite samples, whereas compared to the pure PPy sample there is a decrease in DC conductivity. On the contrary, the magnetic permeability of the composites is higher than that of the pure PPy sample and lower than that of the pure ferrite samples as was expected.     

Structural and some magnetic properties of manganese-substituted lithium ferrites

The structural and magnetic properties of Mn-substituted lithium ferrites having the general formula Li_0.5−0.5xMn_xFe_2.5−0.5xO₄ (where x=0.0–1.0) prepared by the standard ceramic technique have been studied. Single phase cubic structure is confirmed by X-ray diffractometer. This result demonstrates that the samples are homogeneous, and the sharp peaks reveal that the samples are in crystalline form. The lattice parameter ‘a’ and average grain diameter ‘D’ increase with increasing Mn²⁺ ion substitution. The saturation magnetization and the experimental magnetic moment are found to increase with manganese up to x=0.5 and then tends to decrease for x>0.5. The increase in magnetic moment with manganese is attributed to Neel's two sublattice model according to which the magnetic moment is the vector sum of lattice magnetic moment. The decrease in magnetization for x>0.5 obeys the Yafet–Kittel (Y–K) model. The increase in Y–K angles for x≥0.5 indicates the increased favor for triangle spin arrangements on B-sites. This suggests the existence of canted spin structure in the ferrite system with higher content of Mn. Hystersis loops were measured. The initial permeability μ_i was measured as a function of temperature.     

Mössbauer studies of the surface and bulk magnetic structure of scandium-substituted Ba-M-type hexaferrites

A direct comparison of the magnetic structures of a surface layer and of the bulk of Ba-M-type hexagonal ferrites with iron ions partially replaced by Sc diamagnetic ions (BaFe_12?x Sc_xO₁₉) has been made by simultaneous Mössbauer spectroscopy with detection of gamma rays, characteristic x-ray emission, and electrons. It has been found that, if the magnetic lattice of a Ba-M-type hexagonal ferrite is weakly diluted by Sc diamagnetic ions, a ～300-nm thick macroscopic layer forms on the surface of a BaFe_11.4Sc_0.6O₁₉ crystal, in which the iron-ion magnetic moments are noncollinear with the moments in the bulk. The noncollinear magnetic structure forms in the near-surface layer of BaFe_12?x Sc_xO₁₉ crystals because the exchange interaction energy is additionally reduced by the presence of such a “defect” as the surface. This is the first observation in ferromagnetic crystals of an anisotropic surface layer whose magnetic properties, as predicted by Néel, differ from those of the bulk.     

Control of the properties of Pb(TixZr1-x )O3 solid solutions by external disturbances

The influence of x-ray irradiation to absorbed radiation doses D = (0.5?12) × 10⁸ rad on the properties of ferroelectric ceramic Pb(Ti_xZr_1?x )O₃ solid solutions with compositions close to the morphotropic phase boundary was studied. The effects of x-ray radiation on the electrical conductivity of ferroelectric ceramics are shown to differ with x ranging from 0.42 to 0.60. Using empirical equations and numerical techniques, quantitative relations are established between the composition, absorbed radiation dose, and electrical conductivity for Pb(Ti_xZr_1?x )O₃.     

Correlation of defect structure and ionic conductivity in δ-phase solid solutions in the Bi3NbO7–Bi3YO6 system

Defect structure and conductivity behaviour are discussed in the solid solution Bi₃Nb_1−xY_xO_7−x(0.0 ≤ x ≤ 1.0). Investigations were carried out using a combination of ac impedance spectroscopy and powder X-ray and neutron diffraction. Low temperature conductivity and activation energy both increase as a function of x. The former is attributed to an increase in oxide ion vacancy concentration, whereas the latter is due a redistribution of oxide ion vacancies as determined by neutron diffraction measurements. The defect structures at room temperature and 800 °C are presented. Curvature in Arrhenius plots of conductivity throughout the composition range is associated with a temperature dependent redistribution of oxide ions.     

Surface magnetism of Al-substituted Sr-M-type hexagonal ferrites

The surface and bulk magnetic structures of Sr-M-type single-crystal hexagonal ferrites (with the chemical formula SrFe_12?x Al_xO₁₉) have been directly compared by simultaneous gamma, x-ray, and electron Mössbauer spectroscopy. It was found, that when the magnetic lattice of Sr-M hexagonal ferrites is slightly diluted by diamagnetic Al ions, namely, for x=1.8 (SrFe_10.2Al_1.8O₁₉), a ～300-nm thick macroscopic anisotropic layer forms on the crystal surface, wherein iron-ion magnetic moments are oriented differently from those in the bulk of the sample. The reason for the onset of a noncollinear magnetic structure in the surface layer of SrFe_10.2Al_1.8O₁₉ crystals is the additional lowering of the exchange interaction energy caused by the presence of such a “defect” as the surface. Thus an anisotropic surface layer predicted theoretically by L. Néel in 1954 has been detected in ferromagnetic crystals.