Muon-spin-relaxation investigation of EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript>

The magnetic properties of the EuMn₂O₅ multiferroic (samples consisting of single crystals and ceramic samples) have been investigated by the muon-spin-relaxation (μSR) method in the temperature range of 10–300 K. Below the magnetic ordering temperature T _N = 40 K, the loss of the polarization of muons and the effect of the external magnetic field have been observed. Both phenomena can be explained by an additional channel of the depolarization of muons owing to the appearance of muons in a medium with a low electron density due to the charge separation process (the redistribution of the electron density in the phase transition process). The “memory” phenomenon has been revealed in a sample in the external magnetic field; the memory relaxation time depends on the size of the structure units of the samples (single crystals or ceramic grains).     

Study on the spin-states of cobalt-based double-layer perovskite Sr<Subscript>2</Subscript>Y<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Co<Subscript>2</Subscript>O<Subscript>7</Subscript>

The spin-states of cobalt based perovskite compounds depend sensitively on the valence state and local crystal environment of Co ions and the rich physical properties arise from strong coupling among charge, spin, and orbital degrees of freedom. While extensive studies have been carried out in the past, most of them concentrated on the isotropic compound LaCoO₃. In this paper, using the unrestricted Hartree-Fock approximation and the real-space recursion method, we have investigated the competition of various magnetically ordered spin-states of anisotropic double-layered perovskite Sr₂Y_0.5Ca_0.5Co₂O₇. The energy comparison among these states shows that the nearest-neighbor high-spin-intermediate-spin ferromagnetically ordered state is the relevant magnetic ground state of the compound. The magnetic structure and sizes of magnetic moments are consistent with the recent experimental observation.     

Synthesis and electrocatalytic activities of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocubes

In this article, a hydrothermal method was developed to synthesize Co₃O₄ nanocubes using hydrogen peroxide (H₂O₂) as oxidant, Co(NO₃)₂·6H₂O as a cobalt source. The products are characterized in detail by multiform techniques including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are Co₃O₄ nanocubes with size ranging between 20 and 40 nm. The effects of the hydrogen peroxide concentration on the size of the products have been studied. The electrocatalytic activities of H₂O₂ reduction on Co₃O₄ nanocubes in phosphate buffer were also evaluated.     

Magnetic properties of aerugite Co<Subscript>10</Subscript>Ge<Subscript>3</Subscript>O<Subscript>16</Subscript>

This paper reports on the first study of the temperature and field dependences of the magnetization, heat capacity, and electrical properties of synthesized polycrystalline samples of aerugite Co₁₀Ge₃O₁₆, as well as on x-ray diffraction analysis of this compound. It is shown that the cobalt ions in this compound occupy three nonequivalent positions. The results of the experimental and theoretical studies suggest that aerugite is a ferrimagnet with two uncompensated magnetic moments of the cobalt atom per formula unit.     

Structural and magnetic phase transformations in the BiFeO<Subscript>3</Subscript>-CaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> system

The crystal structure and magnetic properties of the Bi_{1 ? x} Ca _x Fe_{1 ? x/2}Nb _x/2O₃ system were studied. It is shown that, at x ≤ 0.15, the unit-cell symmetry of solid solutions is rhombohedral (space group R3c). Solid solutions with x ≥ 0.3 have an orthorhombic unit cell (space group Pbnm). The rhombohedral compositions are antiferromagnetic, while the orthorhombic compositions exhibit a small spontaneous magnetization due to Dzyaloshinski?-Moriya interaction. In CaFe_0.5Nb_0.5O₃, the Fe³⁺ and Nb⁵⁺ ions are partially ordered and the unit cell is monoclinic (space group P2₁/n). In the concentration range 0.15 < x < 0.30, a two-phase state (R3c + Pbnm) is revealed.     

Nanostructured multiferroic PbFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> and its physical properties

Polycrystalline multiferroic PbFe_0.5Nb_0.5O3 (PFN) fabricated by a solid-phase method is studied. Before sintering, a synthesized PFN powder is processed in Bridgman anvils via a force action in combination with shear deformation (FASD) at room temperature. The electrophysical properties and structural parameters of processed samples and a reference sample are compared. Point defects are shown to play a key role in the formation of the physical properties beginning from an FASD of 200 MPa.     

Spin-wave resonances in Eu<Subscript>0.8</Subscript>Ce<Subscript>0.2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>5</Subscript> and EuMn<Subscript>2</Subscript>O<Subscript>5</Subscript> multiferroics

Spin-wave resonances have been observed in superlattices arising due to the phase separation and self-organization of charge carriers in Eu_0.8Ce_0.2Mn₂O₅ single crystals. The resonances are found within the 5–80 K temperature range at frequencies close to 30 GHz. Similar resonances with intensities about an order of magnitude lower are also observed in EuMn₂O₅. The latter suggests the existence of charge transfer processes between the manganese ions of different valences in EuMn₂O₅.     

Synthesis,characterization and magnetic properties of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanotubes

Well-aligned Co₃O₄ nanotubes were synthesized within the nanochannels of porous anodic alumina membranes using a single-source chemical vapor deposition method. Scanning electron microscopy and transmission electron microscopy showed that the Co₃O₄ nanotubes are highly ordered with uniform diameter in the range of 100–300 nm and length up to tens of microns. X-ray diffraction, the Raman spectrum, energy-dispersive spectroscopy and selected-area electron diffraction demonstrated that the nanotubes are composed of pure cubic phase polycrystalline Co₃O₄. Magnetic measurements using a SQUID magnetometer suggested the presence of a strong antiferromagnetic interaction with Weiss constant θ= -248 K. The real and imaginary parts of the ac susceptibility at f= 10 Hz had a maximum at 4.0 K, and the field dependence of the magnetization at 1.8 K showed a small hysteresis loop with a coercivity of ∼ 98 Oe. PACS 81.07.De; 81.15.Gh; 78.30.-j; 75.75.+a; 61.46.Np     

Properties of the ferroelectric ceramics PbSc<Subscript>0.5</Subscript>Ta<Subscript>0.5</Subscript>O<Subscript>3</Subscript> fabricated from an ultradispersed powder

The relaxor ceramics PbSc_0.5Ta_0.5O₃ produced from an ultradispersed powder is studied by X-ray diffraction and dielectric measurements. Before sintering, the powder was subjected to treatment in Bridgman anvils in combination with shear deformation. This method is shown to affect the order parameter and dielectric properties of the ceramics without using long-term high-temperature annealing.     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

Single crystal neutron diffraction study of the magnetisation process in Ca<Subscript>3</Subscript>Co<Subscript>2</Subscript>O<Subscript>6</Subscript>

We have performed neutron diffraction measurements on a single crystal sample of Ca₃Co₂O₆ both in a zero field and in an applied magnetic field. The measurements have revealed details of the zero-field structure of this geometrically frustrated Ising-like spin-chain compound at low temperatures and have also allowed us to examine its magnetisation process. Transitions to the M=M_sat/3 ferrimagnetic state and fully polarised ferromagnetic state have been observed. The neutron scattering results are compared with the magnetisation data, where these transitions are accompanied by the appearance of several steps and plateaux.     

Acacia gum-assisted co-precipitating synthesis of LiNi<Subscript>0.5</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.3</Subscript>O<Subscript>2</Subscript> cathode material for lithium ion batteries

LiNi_0.5Co_0.2Mn_0.3O₂ particles of uniform size were prepared through carbonate co-precipitation method with acacia gum. The precursor of carbonate mixture was calcined at 800 °C, and a well-crystallized Ni-rich layered oxide was got. The phase structure and morphology were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The micro-sized particles delivered high initial discharge capacity of 164.3 mA h g^?1 at 0.5 C (1 C?=?200 mA g^?1) between 2.5 and 4.3 V with capacity retention of 87.5 % after 100 cycles. High reversible discharge capacities of 172.4 and 131.4 mA h g^?1 were obtained at current density of 0.1 and 5 C, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were performed to further study the LiNi_0.5Co_0.2Mn_0.3O₂ particles. Anyway, the excellent electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ sample should be attributed to the use of acacia gum.     

Conductivity of nanostructured India oxide films containing Co<Subscript>3</Subscript>O<Subscript>4</Subscript> or ZrO<Subscript>2</Subscript>

The effect of additives of cobalt and zirconium oxides on the conductivity of nanostructured composites based on indium oxide is studied. It is shown that addition of up to 20 wt % ZrO₂ to In₂O₃ leads to a sharp decrease in the conductivity of the composite. For the Co₃O₄?In₂O₃ system, the conductivity decreases up to a Co₃O₄ content of 60 wt %, after which it increases. At a Co₃O₄ content in the Co₃O₄?In₂O₃ system of up to 60 wt %, n-type conduction takes place, changing to p-type at 80 to 100 wt % Co₃O₄. Zirconium oxide exhibits practically no n-type conduction, so electric current in the ZrO₂?In₂O₃ system flows through In₂O₃ nanocrystals, i.e., n-type conduction takes place. Possible causes of the observed effects are considered.     

Enhanced electrochemical properties and thermal stability of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by surface modification with Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>

Layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode material is synthesized via a sol-gel method and subsequently surface-modified with Eu₂O₃ layer by a wet chemical process. The effect of Eu₂O₃ coating on the electrochemical performances and thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂@Eu₂O₃ cells is investigated systematically by the charge/discharge testing, cyclic voltammograms, AC impedance spectroscopy, and DSC measurements, respectively. In comparison, the Eu₂O₃-coated sample demonstrates better electrochemical performances and thermal stability than that of the pristine one. After 100 cycles at 1C, the Eu₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode demonstrates stable cyclability with capacity retention of 92.9 %, which is higher than that (75.5 %) of the pristine one in voltage range 3.0–4.6 V. Analysis from the electrochemical measurements reveals that the remarkably improved performances of the surface-modified composites are mainly ascribed to the presence of Eu₂O₃-coating layer, which could efficiently suppress the undesirable side reaction and increasing impedance, and enhance the structural stability of active material.     

Structural and magnetic properties of layered Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> thin films

Layered cobalt oxides Ca₃Co₄O₉ thin films have been grown directly on c-cut sapphire substrates using pulsed laser deposition. X-ray diffraction and transmission electron microscopy characterizations show that the deposited films present the expected monoclinic structure and a texture along the direction perpendicular to the Al₂O₃(001) plane. The Ca₃Co₄O₉ structure presents six variants in the film plane. Rutherford backscattering spectroscopy shows that the films are stoichiometric and that the film thickness agrees with the nominal value. The susceptibility χ of the films, recorded along the c-axis of the substrate, after field cooling and zero field cooling in an applied field of 1 kOe shows two magnetic transitions at 19 and 370 K which agree well with previous findings on single crystal samples. In turn, at low temperature (5 K), the magnetization curve along the c-axis exhibits coercive field and remanent magnetization much smaller than those reported for bulk samples, which can be related to the influence of structural variants and structural defects.     

On the correlation between supercooling,superheating and kinetic arrest in a magnetic glass Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>Mn<Subscript>0.975</Subscript>Al<Subscript>0.025</Subscript>O<Subscript>3</Subscript>

We report a quantitative investigation of the magnetic field-temperature phase diagram by taking into account a simple phenomenological model arising out of the interplay of kinetic arrest and thermodynamic transitions in a magnetic glass Pr_0.5Ca_0.5Mn_0.975Al_0.025O₃, through magnetization measurements. Such studies are necessary as kinetic arrest plays an important role in the formation of “magnetic glasses”, which has been observed in systems undergoing first order magnetic phase transitions. It has been shown that disorder in a system results in the formation kinetic arrest (H _K ,T _K ) band, like supercooling (H ^*,T ^*) and superheating (H ^**,T ^**) band. Quantitative proofs are given to show that (H _K ,T _K ) band is anticorrelated with (H ^*,T ^*) and (H ^**,T ^**) bands, while the later two are correlated among themselves. Analysis of time dependence of magnetization at different temperatures is carried out to establish the fact that the kinetic arrested state is different from the supercooled state.     

Formation of three-dimensional arrays of magnetic clusters NiO,Co<Subscript>3</Subscript>O<Subscript>4</Subscript>, and NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> by the matrix method

A method has been proposed for the formation of three-dimensional arrays of isolated magnetic clusters NiO, Co₃O₄, and NiCo₂O₄ in the sublattice of pores in the matrix of bulk synthetic opals through a single impregnation of the pores with melts of nickel and cobalt nitrate crystal hydrates and their thermal degradation. The method makes it possible to controllably vary the degree of filling of pores in the matrix with oxides within 10–70 vol %. The composition and structure of the synthesized materials, as well as the dependences of their static magnetic susceptibility on the magnetic field strength, have been investigated.     

Anisotropy of the Complex Permittivity of the Kagome-Staircase Compounds Co<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> and Ni<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript>: Experiment and Ab Initio Calculations

The anisotropy of the components of the complex permittivity of vanadate Co₃V₂O₈ and Co₃V₂O₈ single crystals in the paramagnetic phase are studied by optical ellipsometry in the spectral region 0.5–5.0 eV. Our experimental results support the weak anisotropy of the optical response detected earlier for axes a and c. The optical properties are also investigated along axis b. The properties of both compounds are compared. The optical spectra of both compounds along axis b are shifted toward low energies as compared to axes a and c. The maximum of the main interband absorption band of Co₃V₂O₈ is shifted toward low energies by 0.25–0.3 eV as compared to Co₃V₂O₈. The electronic structure parameters of both compounds are determined. Optical function spectra are analyzed using the results of ab initio band calculations.     

Dielectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)(Nb<Subscript>0.93</Subscript>Sb<Subscript>0.07</Subscript>)O<Subscript>3</Subscript> ferroelectric ceramics modified with BaTiO<Subscript>3</Subscript>

Processes of the polarization and repolarization of ferroelectric ceramics based on potassium sodium niobate in the region of infralow frequencies are discussed. The effect aging and subsequent annealing in a strong alternating electric field have on the nonlinearity of the dielectric response of a sample at different temperatures is determined.     

Short-Range Order in Amorphous and Crystalline Ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The microstructures of amorphous and polycrystalline ferroelectric Hf_0.5Zr_0.5O₂ films are studied by X-ray spectroscopy and ellipsometry. EXAFS spectra demonstrate that the amorphous film consists of an “incompletely mixed” solid solution of metallic oxides HfO₂ and ZrO₂. After rapid thermal annealing, the mixed Hf_0.5Zr_0.5O₂ oxide films have a more ordered polycrystalline structure, and individual Hf and Zr monoxide islands are formed in the films. These islands are several nanometers in size and have a structure that is similar to the monoclinic structure of HfO₂ and ZrO₂. The presence of the HfO₂ and ZrO₂ phases in the Hf_0.5Zr_0.5O₂ films is also detected by ellipsometry.