Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

Effect of Fe3+ doping on structural,optical and electrical properties δ-Bi2O3 thin films

Fe³⁺ doped δ-Bi₂O₃ thin films were prepared by sol–gel method on quartz glass substrate at room temperature and annealed at 800 °C. The thin films were then characterized for structural, surface morphological, optical and electrical properties by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), optical absorption measurements and d.c. two-probe, respectively. The XRD analyses revealed the formation δ-Bi₂O₃ followed by a mixture of Bi₂₅FeO₄₀ and Bi₂Fe₄O₉. SEM images showed reduction in grain sizes after doping and the optical studies showed a direct band gap which reduced from 2.39 eV for pure δ-Bi₂O₃ to 1.9 eV for 10% Fe³⁺ doped δ-Bi₂O₃ thin film. The electrical conductivity measurement showed the films are semiconductors.     

Dielectric and piezoelectric properties of Fe2O3-doped (Na0.5K0.5)0.96Li0.04Nb0.86Ta0.1Sb0.04O3 lead-free ceramics

The effect of a small amount Fe₂O₃ (0.1-2 mol%) doping on the electrical properties of (Na_0.5K_0.5)_0.96Li_0.04Nb_0.86Ta_0.1Sb_0.04O₃ (NKLNTS) ceramics was investigated. It was found that the B-site substitution of Fe³⁺ does not change the crystal structure within the studied doping level and all modified ceramics have a pure tetragonal perovskite structure at room temperature. The addition of Fe₂O₃ can promote the sintering of NKLNTS ceramics, and simultaneously cause the grain growth so that Fe³⁺-doped NKLNTS compositions show degraded densification at higher doping level. Furthermore, the dielectric properties of the NKLNTS ceramics do not show a significant change by Fe₂O₃ doping. However, the addition of Fe₂O₃ was found to have a significant influence on the electric fatigue resistance and the durability against water. The presence of oxygen vacancies caused by the replacement of Fe³⁺ for B-site ions makes the NKLNTS ceramics harder.     

Improved stability of La0.5Sr0.5FeO3 by Ta-doping for oxygen separation membrane application

(La,Sr)FeO₃ mixed conducting perovskites are considered as interesting candidates for oxygen separation membranes but they suffer from limited structural stability in a large oxygen partial pressure (pO₂) gradient, because of their propensity for chemical expansion. Partial substitution of Fe with more stable elements tends to improve the stability while penalizing the electronic and ionic conductivities.In this study, we investigate the effect of 10% Ta substitution on the oxygen transport properties and stability of La_0.5Sr_0.5FeO₃. For this purpose, the material was evaluated as a membrane in a CPOX reactor. The oxygen permeation through a ~ 3 cm² pellet sample was first measured under air/Ar gradient in the temperature range of 800 to 1000 °C. The measured flux was 0.1 µmol cm^? 2 s^? 1 at 900 °C, which was a factor of 2 lower than for the Ta-free material. Methane was then introduced into the system and reacted in a catalytic bed with oxygen that has permeated through the membrane to form syngas (H₂, CO). As a result, the oxygen flux increased by a factor of 9, reaching 0.9 µmol cm^? 2 s^? 1 at 900 °C. The reactor was operated at 1000 °C for another 1000 h. During this time, the oxygen permeation flux decayed by ca. 4%/1000 h.The test was stopped after more than 2000 h of operation and the membrane analyzed by electron microscopy.     

Preparation of LSGM powders for low temperature sintering

La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 powders were prepared by carbonate coprecipitation and the tuning of the cation composition by a solid state reaction. The relative compositions of La, Sr, Ga, and Mg were dependent upon the supersaturation ratio (R = [(NH₄)₂CO₃]/([La³⁺] + [Sr²⁺] + [Ga³⁺] + [Mg²⁺])) during the coprecipitation. The coprecipitation of a Sr-deficient source solution and the subsequent replenishment of SrO and MgO by ball milling were effective for accomplishing a phase-pure La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 specimen by low-temperature sintering.     

Cation self-diffusion in LaFeO3 measured by the solid state reaction method

Cation diffusion in LaFeO₃ has been studied using the solid state reaction between sintered bodies of La₂O₃ and Fe₂O₃ at 950–1350 °C in air or O₂–N₂ mixtures. LaFeO₃ was the only product formed. The growth was parabolic and demonstrated to take place predominantly by diffusion of Fe³⁺ through the LaFeO₃ layer. The self-diffusion coefficient of Fe³⁺ was accordingly calculated from the parabolic rate constant, and at constant activity of La₂O₃, a_La2O3 = 1, it shows Arrhenius-type behaviour with activation energy 320 ± 20 kJ/mol. It appeared to be independent of the surrounding pO₂, but this was ascribed to lack of equilibrium with the atmosphere during growth of the LaFeO₃ layer. Correspondingly, the product LaFeO₃ is probably stoichiometric, and differences between our diffusivity and activation energy and those in the literature are discussed in view of this.     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Ab-initio study of Sr-doping effects on nitric oxide adsorption on the LaO (001) surface of LaFeO3

Density-functional calculations of molecular nitric oxide (NO) on defective (La,Sr)O (001) surfaces of (La,Sr)FeO_3 ? δ using slab models are performed to elucidate the oxygen vacancy formation problem on the LaO (001) surface of LaFeO_3 ? δ.From the estimation of the NO adsorption energy, NO adsorption is found on (La,Sr)O surfaces of (La_0.83,Sr_0.17)FeO_3 ? δ with δ = 0 or 0.25.The absolute value of the NO adsorption energy shows a remarkable increase at oxygen vacancies in the top surface layer, where the nitrogen atoms of the adsorbed molecules are embedded in the first (La,Sr)O layer, because a bond with Fe in the second FeO₂ layer is formed.Our data shows that Sr doping promotes formation of oxygen vacancies, which keep the NO adsorption ability high.Thus, we conclude that if Sr doping increases the number of oxygen vacancy sites by a charge compensation effect, NO adsorption on LaFeO₃ is enhanced, which provides an explanation for several experimental observations.     

Thermal and chemical expansion of mixed conducting La0.5Sr0.5Fe1−xCoxO3−δ materials

Oxygen deficiency, thermal and chemical expansion of La_0.5Sr_0.5Fe_1−xCo_xO_3−δ (x = 0, 0.5, 1) have been measured by thermogravimetry, dilatometry and high temperature X-ray diffraction. The rhombohedral perovskite materials transformed to a cubic structure at 350 ± 50 °C. The thermal expansion of the materials up to the onset of thermal reduction was 14–18 × 10^− 6 K^− 1. Above 500 °C in air (400 °C in N₂), chemical expansion contributed to the thermal expansion and the linear thermal expansion coefficients were significantly higher, 16–35 × 10^− 6 K^− 1. The chemical expansion, ε_c, showed a maximum of 0.0045 for x = 0.5 and 0.0041 for x = 1 at 800–900 °C. The normalized chemical expansion, ε_c/Δδ, was 0.036 for x = 0.5 and 0.035 for x = 1 at 800 °C. The chemical expansion can be correlated with an increasing ionic radius of the transition metals with decreasing valence state.     

Electrochemical characterization of mixed conducting and composite SOFC cathodes

The electrochemical performance of La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (L58SCF), La_0.9Sr_1.1FeO_4−δ (LS2F) and LSM (La_0.65Sr_0.3MnO_3−δ)/LSM–YSZ (50 wt.% LSM–50 wt.% ZrO₂ (8 mol% Y₂O₃)) cathode electrodes interfaced to a double layer Ce_0.8Gd_0.2O_2−δ (CGO)/YSZ electrolyte was studied in the temperature range of 600 to 850 °C and under flow of 21% O₂/He mixture, using impedance spectroscopy and current density–overpotential measurements. The L58SCF cathode exhibited the highest electrocatalytic activity for oxygen reduction, according to the order: LS2F/CGO/YSZ ≤ LSM/LSM–YSZ/CGO/YSZ < L58SCF/CGO/YSZ.     

The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass

Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ (in mole%) glasses were prepared by the traditional melting–quenching method. The spectroscopic properties and mechanism of NIR broadband emission in these glasses were investigated in this work. Three excitation wavelengths of 500, 700 and 800 nm were used to test emission spectra. The emission band under 500 nm excitation can be regarded as combination of emission bands under 700 and 800 nm excitation. 2.0 mole% is found to be the optimal Bi₂O₃ doping level in this glass. Under 500 nm excitation its emission peak, FWHM and lifetime of emission band are 1160 nm, 300 nm and 569 μs, respectively. The longest fluorescent lifetime reaches 620 μs under 700 nm excitation. The valence state of Bi in these glasses is suggested to be lower than +3 by X-ray photoelectron spectroscopy. With the help of energy matching, we infer that both Bi⁰ and Bi⁺ centers are responsible for the NIR fluorescence of Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ glass.     

Luminescence study of cerium-doped La2Hf2O7: Effects due to trivalent and tetravalent cerium and oxygen vacancies

X-ray excited emission spectra, photoluminescence excitation and emission spectra, optical reflectivity spectra, and pulsed X-ray and optical excited luminescence decay measurements are reported for cerium-doped La₂Hf₂O₇ powders prepared by solid state synthesis. A broad luminescence associated with oxygen vacancies is observed in the region 350–750 nm with a peak around 460 nm. The photoluminescence spectra and the number of oxygen vacancies vary for samples annealed in oxidizing or reducing atmospheres and with the temperature of the synthesis process. Increasing the cerium concentration reduces the oxygen-vacancy-related emission due to the presence of Ce⁴⁺. First principles calculations predict that Ce⁴⁺ can substitute in Hf sites; this is confirmed from the optical reflectivity spectrum of cerium-doped La₂Hf₂O₇. Photoluminescence excitation and emission spectra characteristic of Ce⁴⁺ charge transfer transitions and possibly Ce³⁺ are also observed. Although trivalent cerium may be present, no emission observed from cerium-doped La₂Hf₂O₇ can be attributed to Ce³⁺ in La sites.     

High-temperature compressive creep behaviour of the perovskite-type oxide Ba0.5Sr0.5Co0.8Fe0.2O3 − δ

Compressive creep tests have been performed on perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ ceramics. The activation energy, stress exponent and inverse grain size exponent of the steady-state creep rates are evaluated at p(O₂) = 0.21 ? 10⁵ Pa and 0.01 ? 10⁵ Pa in the stress, temperature and grain size ranges 5–20 MPa, 1078–1208 K and 2.5–17.4 µm, respectively. The results indicate that the creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ is controlled by diffusion of cations via both the oxide lattice (bulk diffusion) and along grain boundaries. The creep rate of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 ? δ increases profoundly by more than one order of magnitude at 1153–1178 K, which is tentatively linked with the onset of the hexagonal-to-cubic phase transition in this compound.     

Peculiarities of luminescent properties of cerium doped YAG transparent nanoceramics

Optical and luminescence properties of transparent nanosized cerium doped Y₃Al₅O₁₂ (YAG:Ce) ceramics have been studied. YAG:Ce nanoceramics were obtained by means of low temperature and high pressure (LTHP) sintering method. Nanoceramic samples were sintered in the 2–8 GPa pressure range, whereas Ce³⁺ concentration was varied in the 0.5–5 at. % range. It is shown that, in contrast to the single crystal, a strong rise of absorption coefficient was detected already at wavelength shorter than 400 nm in all nanoceramic samples studied. Furthermore, in nanoceramic samples unusual UV emission band near 3.1 eV was observed, which is not observed in the YAG:Ce single crystal. High pressure applied during nanoceramics sintering leads to significant changes in their optical and luminescence properties.     

Synthesis and characterization of CaLaFe11O19

A new ferrimagnetic compound with the chemical formula CaLaFe₁₁O₁₉ has been synthesized by solid state reaction between the respective oxides and their structural, electrical and magnetic properties have been studied. One magnetic Fe³⁺ ion in CaLaFe₁₂O₁₉ is replaced by La³⁺ ion. The crystallographic results show the compound is hexagonal magnetoplumbite. The electrical conductivity has been measured from 300 to 800 K. The activation energy changes at Curie temperature (653 K). The compound is ferrimagnetic from 300 to 653 K and above T_c it acts as a paramagnetic. Variation of inverse molar susceptibility has been measured at various temperature in paramagnetic region and Curie molar constant (C_m) is calculated. AC susceptibility measurements are made at room temperature. The Seebeck coefficient (S) measurements show that the compound is n-type.     

Electrical conductivity and thermal expansion of La0.8Sr0.2(Mn,Fe,Co)O3-δ perovskites

La_1−xSr_xMeO₃ (Me = Mn, Co, Fe) perovskites are used as cathodes and are also attractive materials for application as the contact layer between cathode and interconnect in solid oxide fuel cells. In this contribution, three perovskite series, La_0.8Sr_0.2Mn_1−xCo_xO_3-δ (series 1), La_0.8Sr_0.2Fe_1−xCo_xO_3-δ (series 2) and La_0.8Sr_0.2Mn_1−x/2Fe_(1−x)/2Co_xO_3-δ (series 3) with x = 0, 0.25, 0.5, 0.75 and 1 were re-investigated under identical synthesis and measurement conditions with the aim of obtaining a full overview of the quasi-ternary system La_0.8Sr_0.2MnO_3-δ–La_0.8Sr_0.2FeO_3-δ–La_0.8Sr_0.2CoO_3-δ. The distribution of the different crystallographic phases in the selected series, the DC electrical conductivity and the thermal expansion coefficients are presented.     

La0.75Sr0.25Cr0.5Mn0.5O3−δ + Cu composite anode running on H2 and CH4 fuels

La_1−xSr_xCr_1−xM_xO_3−δ (M = Cr, Fe, V) system has been studied as anode materials for solid oxide fuel cells (SOFCs). The perovskite La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) is stable in both H₂ and CH₄ atmospheres at temperatures up to 1000°C. However, in the reducing atmospheres of H₂ and CH₄, its electronic conductivity is greatly reduced from its value in air. We have characterized LSCM as the anode of a SOFC having 250 μm-thick La_0.8Sr_0.2Ga_0.83Mg_0.17O_2.815 (LSGM) as the electrolyte and SrCo_0.8Fe_0.2O_3−δ (SCF) as the cathode. We report a comparison of the overpotentials at the following anodes: (1) La_0.4Ce_0.6O_1.8 (LDC) + NiO composite in H₂, (2) porous LSCM in H₂ and CH₄, (3) porous LSCM impregnated with CuO in H₂ and CH₄ and (4) porous LSCM impregnated with CuO and sputtered with Pt in H₂ and CH₄. An LSCM + CuO + Pt anode gave a maximum power output at 850 °C of 850 mW/cm² and 520 mW/cm², respectively, with H₂ and CH₄ as fuel whereas anode (1) gave 1.4 W/cm² at 800 °C in H₂. There was no noticeable coke formation in CH₄ with anodes (2), (3) and (4), which demonstrates that the perovskite oxide is a plausible option for the anode of a SOFC operating with hydrocarbon fuels. We also report the moisture effect in the H₂ and CH₄ fuel-oxidation process.     

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.     

Structural,morphological, magnetic and dielectric characterization of nano-phased antimony doped manganese zinc ferrites

Nano-phased doped Mn–Zn ferrites, viz., Mn_0.5−x/2Zn_0.5−x/2Sb_XFe₂O₄ for x=0 to 0.3 (in steps of 0.05) prepared by hydrothermal method are characterized by X-ray diffraction, Infrared and scanning electron microscopy. XRD and SEM infer the growth of nano-crystalline cubic and hematite (α-Fe₂O₃) phase structures. IR reveals the ferrite phase abundance and metal ion replacement with dopant. Decreasing trend of lattice constant with dopant reflects the preferential replacement of Fe³⁺ions by Sb⁵⁺ion. Doping is found to cause for the decrease (i.e., 46–14 nm) of grain size. An overall trend of decreasing saturation magnetization is observed with doping. Low magnetization is attributed to the diamagnetic nature of dopant, abundance of hematite (α-Fe₂O₃) phase, non-stoichiometry and low temperature (800 °C) sintering conditions. Increasing Yafet–Kittel angle reflects surface spin canting to pronounce lower M_s. Lower coercivity is observed for x≤0.1, while a large H_c results for higher concentrations. High ac resistivity (~10⁶ ohm-cm) and low dielectric loss factor (tan δ~10⁻²–10⁻³) are witnessed. Resistivity is explained on the base of a transformation in the Metal Cation-to-Oxide anion bond configuration and blockade of conductivity path. Retarded hopping (between adjacent B-sites) of carriers across the grain boundaries is addressed. Relatively higher resistivity and low dielectric loss in Sbdoped Mn–Zn ferrite systems pronounce their utility in high frequency applications.     

Structure and magnetic properties of the intermetallic La2Co17−xMox (x=0.5, 1, 1.5, 2) and La2Co16−yFeyMo (y=0, 1, 2, 3, 4, 6) compounds

The effect of Mo and Fe atoms on the crystal structure and magnetic properties of the intermetallic La₂Co_17−xMo_x (x=0.5, 1, 1.5, 2), and La₂Co_16−yFe_yMo (y=0, 1, 2, 3, 4, 6) compounds have been studied by X-ray diffractometry, magnetic measurements and Mössbauer spectroscopy. All samples belong to the rhombohedral Th₂Zn₁₇-type structure and their lattice parameters a and c increase both with Mo and Fe content. From the La–Co–Mo samples only the one with x=0.5 presents planar anisotropy, whereas from the La–Co–Fe–Mo samples only the y=1 has uniaxial anisotropy. The magnetization M_S and the Curie temperature T_C decrease upon Mo substitution, whereas the anisotropy field H_A does not change significantly. In the Fe-substituted compounds M_S increases, but the Curie temperature increases slightly for 0⩽y⩽4 but decreases in y=6. The low temperature M–T curve shows that the samples La₂Co_16.5Mo_0.5, and La₂Co₁₀Fe₆Mo present a spin reorientation transitions at 70 and 260 K, respectively. Mössbauer samples were obtained for all Fe-containing samples in the temperature range 20–300 K. Above 260 K a jump in the values of the hyperfine fields and quadrupole splitting parameters is observed which can be associated to the spin reorientation.