Characterisation of the reduction properties of La0.5Sr0.5Fe0.5Co0.5O3

We report here on the characterisation by temperature programmed reduction, ⁵⁷Fe Mössbauer spectroscopy and X-ray absorption spectroscopy of the phases resulting from treatment of the perovskite-related material La_0.5Sr_0.5Fe_0.5Co_0.5O₃ in a flowing 90% hydrogen/10% nitrogen atmosphere. The results show that treatment of La_0.5Sr_0.5Fe_0.5Co_0.5O₃ (which contains approximately 50% Fe⁴⁺ and 50% Fe³⁺) in the flowing 90% hydrogen/10% nitrogen atmosphere at 600°C does not result in the reduction of any of the constituent elements of the material and that the perovskite structure is still retained. The Mössbauer spectrum recorded following heating in the gaseous reducing environment at 1,000°C shows the presence of metallic iron, an Fe³⁺-containing phase with parameters compatible with the presence of SrLaFeO₄ which has a K₂NiF₄-type structure, and a paramagnetic Fe³⁺ phase. The X-ray absorption spectroscopy results show the presence of metallic cobalt. The Mössbauer spectrum recorded following heating at 1,200°C continues to show the Fe³⁺-containing components plus a larger contribution from metallic iron. The X-ray absorption spectroscopy results show the presence of metallic cobalt, SrLaFeO₄, La₂O₃ and SrO.     

Crystal electric field effects in Pr0.5Sr0.5CoO3

The energy structure and temperature evolution of the magnetic excitation spectra of Pr_0.5Sr_0.5CoO₃ are studied by inelastic neutron scattering. The measurements are performed on a polycrystalline sample of Pr_0.5Sr_0.5CoO₃ and its non-magnetic analogue La_0.5Sr_0.5CoO₃ on the high intensity time-of-flight spectrometer IN4 (ILL, Grenoble) in the temperature range 10 K < T < 300 K. The crystal electric field parameters in Pr_0.5Sr_0.5CoO₃ are calculated and the splitting scheme of the 4f ground multiplet of Pr³⁺ ions is determined based on the experimental data.     

Crystal structure and spin state of Fe0.5Co0.5(NCS)2(bpa)2

Fe(NCS)₂(bpa)₂, Co(NCS)₂(bpa)₂, and Fe_0.5Co_0.5(NCS)₂(bpa)₂ were synthesized. X-ray structural analysis revealed that the structure was the same among the three complexes. Although the metal-ligand distance in the mixed crystals was shorter than the distance in Fe(NCS)₂(bpa)₂ and was similar to that in Co(NCS)₂(bpa)₂, the spin state remained temperature-independent Fe^II high-spin state in ⁵⁷Fe M?ssbauer spectra.     

Structure and oxygen stoichiometry of SrCo0.8Fe0.2O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ

High temperature X-ray diffraction (HT-XRD), temperature programmed desorption (TPD), thermogravimetric analysis–differential thermal analysis (TGA/DTA) and neutron diffraction were combined to determine the structure and oxygen stoichiometry of SrCo_0.8Fe_0.2O_3−δ (SCF) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) up to 1273 K in the pO₂ range of 1 to 10^− 5 atm. Formation of the vacancy-ordered brownmillerite phase, SrCo_0.8Fe_0.2O_2.5, was observed as a region of zero oxygen release in the TPD measurements and confirmed by HT-XRD and TGA/DTA. No ordering was observed in the BSCF system by any of the techniques utilized in this work. The oxygen vacancy concentration of BSCF was found to be considerably higher than that of SCF and always higher than that of the ordered brownmillerite phase of SCF, δ = 0.5. The combination of a high vacancy concentration and absence of ordering leads to higher oxygen permeation fluxes through BSCF membranes in comparison to SCF.     

Ba0.5Sr0.5Co0.8Fe0.2O3−δ thin film microelectrodes investigated by impedance spectroscopy

The electrochemical properties of geometrically well-defined Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF) microelectrodes have been investigated by impedance spectroscopy. The microelectrodes of 20–100 μm diameter and 100 nm thickness were prepared by pulsed laser deposition (PLD), photolithography and argon ion beam etching. The oxygen reduction reaction at these model electrodes is limited by interfacial processes, i.e. by the oxygen surface exchange and/or by the transfer of oxide ions across the electrode/electrolyte boundary, whereas the resistance associated with the transport of oxide ions through the bulk of the thin film electrode is negligible. The experiments revealed an extremely low absolute value of the electrochemical surface exchange resistance of only 0.09 (± 0.03) Ω cm² at 750 °C in air, which is more than a factor of 50 lower than the corresponding value measured for La_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (LSCF) microelectrodes of the same geometry. The dependence of this and other electrochemical quantities such as the chemical bulk capacitance or the BSCF/YSZ interfacial resistance on temperature has been studied between 500 and 750 °C.     

Study of Co0.5Zn0.5Fe2O4 nanoparticles for magnetic hyperthermia

Physics of the Solid State - The structural characteristics, magnetic properties, and processes of magnetic heating in an alternating magnetic field of magnetic nanoparticles (MNPs) Co0.5Zn0.5Fe2O4...     

Domain structure of the antiferromagnetic insulating state in Nd0.5Sr0.5MnO3

Optical reflectivity studies of the ferromagnetic metal (FMM) to antiferromagnetic insulator (AFI) phase transition were performed on Nd_0.5Sr_0.5MnO₃ single crystals in a wide temperature and magnetic field range. The formation of a domain structure in the AFI state was observed. On the basis of the experimental results and symmetry analysis we conclude that these domains are crystal twins, confirming the symmetry lowering of the crystal at this phase transition. The twin domain structure of the AFI state in the Nd_0.5Sr_0.5MnO₃ is visible in reflected unpolarized light due to a different tilting of the surface of the domains. We find no evidence for intermediate FMM+AFI stripe phase.     

Low-temperature magnetic properties of HoMn0.5Co0.5O3 single crystals

The magnetic behavior of a HoMn_0.5Co_0.5O₃ single crystal grown by electrochemical deposition was studied by measuring magnetization in the temperature range 5–300 K in magnetic fields of up to 50 kOe. The results obtained are treated within a model of the two-phase magnetic state of a crystal. A comparative analysis of the magnetic properties of HoMn_0.5Co_0.5O₃ and LaMn_0.5Co_0.5O₃ single crystals was carried out.     

First-principles study of electronic structure and magnetic properties of Sr3Fe2O5 oxide

We investigate the electronic structure and magnetic properties of layered compound Sr₃Fe₂O₅ based on first-principles calculations in the framework of density functional theory with GGA+U method. Under high pressure, the ladder-type layered structure of Sr₃Fe₂O₅ is transformed into the infinite layered structure accompanied by a transition from G-type anti-ferromagnetic (AFM) insulator to ferromagnetic (FM) metal and a spin transition from S=2 to S=1. We reproduce these transformations in our calculations and give a clear physical interpretation.     

A study of the magnetic and dielectric properties of Y Fe0.5Cr0.5O3

Y Fe_0.5Cr_0.5O₃ ceramics have been synthesized by a conventional solid-state reaction. Powder X-ray diffraction shows that this compound possesses an orthorhombic structure with Pnma space group. It exhibits a high magnetic transition temperature at around 250 K with weak ferromagnetic behavior below this temperature. A dielectric relaxation following the Arrhenius law found in the Y Fe_0.5Cr_0.5O₃ compound can be attributed to the charge carrier hopping conduction.     

Oxygen permeability and stability of Ba0.5Sr0.5Co0.8Fe0.2O3−δ as an oxygen-permeable membrane at high pressures

Oxygen permeation fluxes across the dense Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) membrane disks were measured under an air/helium oxygen partial pressure gradient at high pressures (up to 10 atm) and various temperatures (973–1123 K). The fabricated BSCFO membrane exhibited good oxygen permeability with a high oxygen permeation flux of 2.01 ml min^− 1cm^− 2 (thickness: 1.37 mm) at 1123 K and 10 atm. Oxygen permeation results were analyzed theoretically using the surface exchange current model. The dependences of the oxygen permeation fluxes on the oxygen partial pressure gradient, suggested that the bulk oxygen ionic diffusion was the rate-limiting step for the overall oxygen permeation process across the BSCFO membrane. The ambipolar diffusion coefficients (D_a), the oxygen vacancy diffusion coefficients (D_v) and the oxygen ionic conductivities (σ_i) of the BSCFO material at different temperatures (973–1123 K) were calculated. It was found that BSCFO possessed high oxygen diffusion coefficients and ionic conductivities, which resulted in the good oxygen permeability of BSCFO. In addition, the BSCFO membrane exhibited good stability of oxygen permeation at 1123 K, while the deterioration of oxygen permeation stability was observed at 1098 K due to structural changes occurring at the surface of the BSCFO membrane disk as demonstrated by XRD.     

Pseudogap behavior in Pr0.5Sr0.5MnO3: A photoemission study

The valence band electronic structure of Pr_0.5Sr_0.5MnO₃ has been investigated across its paramagnetic metallic (PMM)–ferromagnetic metallic (FMM)–antiferromagnetic insulator (AFMI) transition. Using surface sensitive high resolution photoemission we have conclusively demonstrated the presence of a pseudogap of magnitude 80 meV in the near Fermi level electronic spectrum in the PMM and FMM phases and finite intensity at the Fermi level in the charge ordering (CO)-AFMI phase. The pseudogap behavior is explained in terms of the strong electron–phonon interaction and the formation of Jahn Teller (JT) polarons, indicating the charge localizations. The finite intensity at the Fermi level in the insulating phase showed a lack of charge ordering in the surface of the Pr_0.5Sr_0.5MnO₃ samples.     

半掺杂钙钛矿Pr0.5Sr0.5CoO3中磁熵变的标度律研究

对半掺杂氧化钴Pr0.5Sr0.5CoO3在居里温度附近的磁熵变进行了研究。研究表明,磁熵变的最大值依赖于外磁场强度;半高宽也与磁场强度有关;相对制冷能力与磁场强度几乎呈线性关系。另外,在不同的温度和磁场强度下测得的磁熵变能够重新标度为一条普适的曲线。依据该唯象的普适曲线,能够较准确的计算出在不同温度和磁场强度下磁熵变的大小。     

半掺杂钙钛矿Pr_(0.5)Sr_(0.5)CoO_3中磁熵变的标度律研究

对半掺杂氧化钴Pr0.5Sr0.5Co O3在居里温度(TC≈232 K)附近的磁熵变(ΔSM)进行了研究.研究表明,磁熵变的最大值(ΔSmaxM)依赖于外磁场强度(H):ΔSmaxM~Hn,其中n=0.55±0.14;半高宽(δTFWHM)与H有如下关系:δTFWHM~H0.4±0.1;而相对制冷能力(RCP)与H几乎呈线性关系.另外,在不同的温度和磁场强度下测得的磁熵变(ΔSM(T,H))能够重新标度为一条普适的曲线.依据该唯象的普适曲线,能够较准确的计算出在不同温度和磁场强度下磁熵变的大小.     

Electronic structure and properties of strontium ferrite Sr3Fe2O6

The electronic structure of strontium ferrite Sr₃Fe₂O₆ was calculated using the tight-binding linear muffin-tin orbital method (TB LMTO) in the local spin density approximation of density functional theory with Coulomb correlations correction (LSDA+U). The semiconducting character of the spectrum with charge transfer energy gap of 1.82 eV was obtained in reasonably good agreement with experimental data. The iron ions are found to be in the high spin state. The calculated value of the local spin magnetic moment of Fe³⁺ ion is 3.94 μ_B which is not typical for trivalent iron ion in the high spin state. It is shown that the strong hybridization between Fe3d and O2p orbitals favors the d⁶ L configuration of Fe³⁺ ion, where L is a hole in the oxygen p shell. The mechanism of oxygen transport in ferrite is discussed basing on the total energy calculations of the different spatial configurations of oxygen vacancies.     

Structural, magnetic and electrochemical studies on LiCo0.5Fe0.5O2

LiCo_0.5Fe_0.5O₂ was prepared by sol–gel method. The sample had spinel, cubic and hexagonal phases up to 873 K and a single hexagonal phase above 1,073 K. The magnetic properties were studied at room temperature and at 77 K. The large coercivities observed for the samples annealed at 1,073 and 1,273 K show that these samples do not exhibit a simple antiferromagnetic ordering. From the Mössbauer and magnetization measurements, it is concluded that the hexagonal phase is only an antiferromagnet. The above results clearly demonstrate that the simple aqueous-based sol–gel process developed in this work provides a viable method to synthesize the fine cuboidal particles that display discharge capacity as high as ≈165 mAh/g, which is higher than the value obtained by M. Holzapfel et al. (Holzapfel M, Schreiner R, Ott A, Electrochim Acta 46:1063, 2001) for their samples synthesized by using the ion exchange method. This work suggests that the approaches based on solution chemistry are viable processes for synthesizing good quality electrode material.