Influence of Sr substitution on thermoelectric properties of La1−xSrxFeO3 ceramics

Perovskite La_1−xSr_xFeO₃ (0.10 ⩽ x ⩽ 0.20) ceramics have been synthesized by the conventional solid-state reaction technique. Their electrical resistivity, Seebeck coefficient and thermal conductivity have been measured. It has been found that the increase of Sr content reduces significantly both the electrical resistivity and the Seebeck coefficient, but slightly increases the high-temperature thermal conductivity. An adiabatic hopping conduction mechanism of small polaron is suggested from the analysis of the temperature dependence of the electrical resistivity. Seebeck coefficients decrease with increasing temperature, and saturate at temperature above 573 K. The saturated value of Seebeck coefficient decreases with increasing of Sr contents, from 200 μV/K for x = 0.10 to 100 μV/K for x = 0.20. All samples exhibit lower thermal conductivity with values around 2.6 W/m K. The highest dimensionless figure of merit is 0.031 at temperature 973 K in La_0.88Sr_0.12FeO₃.     

A comparative study of the Ruddlesden-Popper series,Lan+1NinO3n+1 (n = 1, 2 and 3), for solid-oxide fuel-cell cathode applications

A comparative investigation of the much-studied La₂NiO_4+δ (n = 1) phase and the higher-order Ruddlesden-Popper phases, La_n+1Ni_nO_3n+1 (n = 2 and 3), has been undertaken to determine their suitability as cathodes for intermediate-temperature solid-oxide fuel cells. As n is increased, a structural phase transition is observed from tetragonal I4/mmm in the hyperstoichiometric La₂NiO_4.15 (n = 1) to orthorhombic Fmmm in the oxygen-deficient phases, La₃Ni₂O_6.95 (n = 2) and La₄Ni₃O_9.78 (n = 3). High temperature d.c. electrical conductivity measurements reveal a dramatic increase in overall values from n = 1, 2 to 3 with metallic behavior observed for La₄Ni₃O_9.78. Impedance spectroscopy measurements on symmetrical cells with La_0.9Sr_0.10Ga_0.80Mg_0.20O_3−δ (LSGM-9182) as the electrolyte show a systematic improvement in the electrode performance from La₂NiO_4.15 to La₄Ni₃O_9.78 with ∼ 1 Ω cm² observed at 1073 K for the latter. Long-term thermal stability tests show no impurity formation when La₃Ni₂O_6.95 and La₄Ni₃O_9.78 are heated at 1123 K for 2 weeks in air, in contrast to previously reported data for La₂NiO_4.15. The relative thermal expansion coefficients of La₃Ni₂O_6.95 and La₄Ni₃O_9.78 were found to be similar at ∼ 13.2 × 10^− 6 K^− 1 from 348 K to 1173 K in air compared to 13.8 × 10^− 6 K^− 1 for La₂NiO_4.15. Taken together, these observations suggest favourable use for the n = 2 and 3 phases as cathodes in intermediate-temperature solid-oxide fuel cells when compared to the much-studied La₂NiO_4+δ (n = 1) phase.     

Luminescence of Eu2+–vc− dipoles and their associates in CsI:Eu crystals

Spectral-kinetics properties of photo-scintillation excited with single light pulses of a nitrogen laser (λ=337.1 nm, t_1/2=5 ns, Q=1 mJ) have been studied in CsI:Eu crystals at temperature within 80–300 K. It is found that the exponential decay of 463 nm emission band has a time constant which grows from 0.85 μs at 78 K to 1.6 μs at 380 K. Such an anomalous temperature behavior of 463 nm emission decay kinetics is discussed in terms of the crystal thermal expansion. It has been proposed that 463 nm emission is caused by a cluster center consisting of three dipoles Eu²⁺v_c^? bounded with each other in a hexagon. Owing to the exchange resonance in the cluster, the energy passes from an excited dipole to a non-excited one and the distance between them gets longer due to thermal expansion of the crystal.     

Phase stability and oxygen non-stoichiometry of SrCo0.8Fe0.2O3−δ measured by in situ neutron diffraction

The phase stability, oxygen stoichiometry and expansion properties of SrCo_0.8Fe_0.2O_3−δ (SCF) were determined by in situ neutron diffraction between 873 and 1173 K and oxygen partial pressures of 5 × 10^− 4 to 1 atm. At a pO₂ of 1 atm, SCF adopts a cubic perovskite structure, space group Pm3¯m, across the whole temperature range investigated. At a pO₂ of 10^− 1 atm, a two-phase region exists below 922 K, where the cubic perovskite phase coexists with a vacancy ordered brownmillerite phase, Sr₂Co_1.6Fe_0.4O₅, space group Icmm. A pure brownmillerite phase is present at pO₂ of 10^− 2 and 5 × 10^− 4 atm below 1020 K. Above 1020 K, the brownmillerite phase transforms to cubic perovskite through a two-phase region with no brownmillerite structure observed above 1064 K. Large distortion of the BO₆ (B = Co, Fe) octahedra is present in the brownmillerite structure with apical bond lengths of 2.2974(4) Å and equatorial bond lengths of 1.9737(3) Å at 1021 K and a pO₂ of 10^− 2 atm. SCF is highly oxygen deficient with a maximum oxygen stoichiometry, 3 − δ, measured in this study of 2.58(2) at 873 K and a pO₂ of 1 atm and a minimum of 2.33(2) at 1173 K and a pO₂ of 5 × 10^− 4 atm. Significant differences in lattice volume and expansion behavior between the brownmillerite and cubic perovskite phases suggest potential difficulties in thermal cycling of SrCo_0.8Fe_0.2O_3−δ membranes.     

Structure,optical spectroscopy and dispersion parameters of ZnGa2Se4 thin films at different annealing temperatures

Thin films of ZnGa₂Se₄ were deposited by thermal evaporation method of pre-synthesized ingot material onto highly cleaned microscopic glass substrates. The chemical composition of the investigated compound thin film form was determined by means of energy-dispersive X-ray spectroscopy. X-ray diffraction XRD analysis revealed that the powder compound is polycrystalline and the as-deposited and the annealed films at T_a = 623 and 673 K have amorphous phase, while that annealed at T_a = 700 K is polycrystalline with a single phase of a defective chalcopyrite structure similar to that of the synthesized material. The unit-cell lattice parameters were determined and compared with the reported data. Also, the crystallite size L, the dislocation density δ and the main internal strain ε were calculated. Analyses of the AFM images confirm the nanostructure of the prepared annealed film at 700 K. The refractive index n and the film thickness d were determined from optical transmittance data using Swanepoel's method. It was found that the refractive index dispersion data obeys the single oscillator model from which the dispersion parameters were determined. The electric susceptibility of free carriers and the carrier concentration to the effective mass ratio were determined according to the model of Spitzer and Fan. The analysis of the optical absorption revealed both the indirect and direct energy gaps. The indirect optical gaps are presented in the amorphous films (as-deposited, annealed at 623 and 673 K), while the direct energy gap characterized the polycrystalline film at 700 K. Graphical representations of ε₁, ε₂, tan δ, ? Im[1/ε*] and ? Im[(1/ε* + 1)] are also presented. ZnGa₂Se₄ is a good candidate for optoelectronic and solar cell devices.     

Recombination luminescence of CsI(Tl) under electron pulse irradiation

The luminescence kinetics of CsI(Tl) exposed to an electron pulse irradiation (E_e = 250 keV, t_1/2 = 10 ns, j = 2 ÷ 160 mJ/cm²) has been studied. It has been discovered that the slow emission rise is due to hole V_k–Tl⁰ recombination luminescence at temperature from 100 to 160 K and electron–V_kA recombination, where electrons released from single Tl⁰ at temperature from 180 to 300 K. The effect of Tl concentration on both processes has been investigated.     

Annealing effects on the crystal structure and physical properties of FeSe1−xTex (0.6 ≦ x ≦ 1) single crystals

Annealing effects of FeSe_1?xTe_x (0.6 ≦ x ≦ 1) single crystals have been investigated from measurements of the powder X-ray diffraction and specific heat. Through the annealing, several peaks of powder X-ray diffraction have become sharp and a clean jump of the specific-heat at the superconducting (SC) transition temperature, T_c, has been observed for x = 0.6–0.9, indicating bulk superconductivity. For annealed single-crystals of x = 0.6–0.8, the SC condensation energy, U₀, and the SC gap, Δ₀, at 0 K have been estimated as ～1.8 J/mol and 2.3–2.5 meV, respectively. The value of 2Δ₀/k_BT_c is 3.9–4.5, indicating a little strong-coupling superconductivity. Both the electronic specific-heat coefficient in the normal state, γ_n, and the residual electronic specific-heat coefficient in the SC state, γ₀, have been found to show significant x dependence. The values of γ_n are much larger than those estimated from the band calculation.     

Mixed conductivity,stability and thermomechanical properties of Ni-doped La(Ga,Mg)O3−δ

Perovskite-type LaGa_0.65Mg_0.15Ni_0.20O_3−δ exhibiting oxygen transport comparable to that in K₂NiF₄-type nickelates was characterized as a model material for ceramic membrane reactors, employing mechanical tests, dilatometry, oxygen permeability and faradaic efficiency measurements, thermogravimetry (TG), and determination of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10^− 15 Pa to 40 kPa. Within the phase stability domain which is similar to La₂NiO_4+δ, the defect chemistry of LaGa_0.65Mg_0.15Ni_0.20O_3−δ can be adequately described by the ideal solution model with oxygen vacancies and electron holes to be the only mobile defects, assuming that Ni²⁺ may provide two energetically equivalent sites for hole location. This assumption is in agreement with the density of states, estimated from thermopower, and the coulometric titration and TG data suggesting Ni⁴⁺ formation in air at T < 1150 K. The hole conductivity prevailing under oxidizing conditions occurs via small-polaron mechanism as indicated by relatively low, temperature-activated mobility. The ionic transport increases with vacancy concentration on reducing p(O₂) and becomes dominant at oxygen pressures below 10^− 7–10^− 5 Pa. The average thermal expansion coefficients in air are 11.9 × 10^− 6 and 18.4 × 10^− 6 K^− 1 at 370–850 and 850–1270 K, respectively. The chemical strain of LaGa_0.65Mg_0.15Ni_0.20O_3−δ ceramics at 1073–1123 K, induced by the oxygen partial pressure variations, is substantially lower compared to perovskite ferrites. The flexural strength determined by 3-point and 4-point bending tests is 167–189 MPa at room temperature and 85–97 MPa at 773–1173 K. The mechanical properties are almost independent of temperature and oxygen pressure at p(O₂) = 1–2.1 × 10⁴ Pa and 773–1173 K.     

Thermoluminescence,infrared reflectivity and electron paramagnetic resonance properties of hemimorphite

Silicate mineral hemimorphite has been investigated concerning its TL, IR and EPR properties. A broad TL peak around 180 °C and a weaker and narrower peak around 360 °C were found in a sample annealed at 600 °C for 1 h and then irradiated. The deconvolution using the CGCD method revealed peaks around 132, 169, 222 and 367 °C. The reflectivity measurements showed several bands in the NIR region due to H₂O, OH and Al–OH complexes. No band was observed in the visible region. The thermal treatments were carried out from ∼110 to 940 °C and dehydration was observed, first causing a diminishing optical absorption in general and the disappearance of water and hydroxyl absorption bands. The EPR spectrum of natural hemimorphite, presented Cu²⁺ signals at g = 2.4 and g = 2.1 plus E₁′ signal superposed to Fe³⁺ signal around g = 2.0.     

Crystal growth and structural properties of the spinel-type Li1 + xMn2 − xO4 (x = 0.10, 0.14)

Single crystals of the lithium-rich lithium manganese oxide spinels Li_1 + xMn_2 − xO₄ with x = 0.10 and 0.14 have been successfully synthesized in high-temperature molten chlorides at 1023 K. The single-crystal X-ray diffraction study confirmed the cubic Fd3¯m space group and the lattice parameters of a = 8.2401(9) Å for x = 0.10 and a = 8.2273(10) Å for x = 0.14 at 300 K, respectively. The crystal structures have been refined to the conventional values R = 3.7% for x = 0.10 and R = 3.1% for x = 0.14, respectively. Low-temperature single-crystal X-ray diffraction experiments revealed that these single crystal samples showed no phase transition between 100 and 300 K. The electron-density distribution images in these compounds by the single-crystal MEM analysis clearly showed strong covalent bonding features between the Mn and O atoms due to the Mn–3d and O–2p interaction.     

Effect of W-addition on pinning property of MgB2

The 5d transition metal W was added into the MgB₂ superconductor. The Mg, B and W were sintered at 1173 K for 30 min under H₂/Ar atmosphere in the electric furnace. The W_x(MgB₂)_1?x samples were prepared in the W concentration range of 0 ? x ? 0.05. Temperature and field dependences of magnetization were measured by the SQUID magneto-meter. The field and x dependences of J_c at 20 K were analyzed by the extended critical state model. The enhancement of J_c became maximum for the x = 0.02 sample.     

Dielectric properties and study of AC electrical conduction mechanisms by non-overlapping small polaron tunneling model in Bis(4-acetylanilinium) tetrachlorocuprate(II) compound

In the present work, the synthesis and characterization of the Bis(4-acetylanilinium) tetrachlorocuprate(II) compound are presented. The structure of this compound is analyzed by X-ray diffraction which confirms the formation of single phase and is in good agreement the literature. Indeed, the Thermo gravimetric Analysis (TGA) shows that the decomposition of the compound is observed in the range of 420–520 K. However, the differential thermal analysis (DTA) indicates the presence of a phase transition at T=363 k. Furthermore, the dielectric properties and AC conductivity were studied over a temperature range (338–413 K) and frequency range (200 Hz–5 MHz) using complex impedance spectroscopy. Dielectric measurements confirmed such thermal analyses by exhibiting the presence of an anomaly in the temperature range of 358–373 K. The complex impedance plots are analyzed by an electrical equivalent circuit consisting of resistance, constant phase element (CPE) and capacitance. The activation energy values of two distinct regions are obtained from log σT vs 1000/T plot and are found to be E=1.27 eV (T<363 K) and E=1.09 eV (363 K<T).The frequency dependence of ac conductivity, σ_ac, has been analyzed by Jonscher's universal power law σ(ω)=σ_dc+Aω^s. The value of s is to be temperature-dependent, which has a tendency to increase with temperature and the non-overlapping small polaron tunneling (NSPT) model is the most applicable conduction mechanism in the title compound.     

Temperature coefficient of resistance and thermal conductivity of Vanadium oxide ‘Big Mac’ sandwich structure

In this paper, we synthesize and characterize a thin film thermometer structure for infrared microbolometers. The structure is composed of alternating multilayers of Vanadium pentoxide (V₂O₅), 25 nm, and Vanadium (V), 5 nm, thin films deposited by rf magnetron and dc magnetron sputtering respectively and annealed for 20, 30 and 40 min at 300 °C in Nitrogen (N₂) atmosphere. The best achieved temperature coefficient of resistance (TCR) was found to be −2.57%/K for 40 min annealed samples. Moreover, we apply, for the first time, the photo-thermal deflection (PTD) technique for measuring the thermal conductivity of the synthesized thin films. The thermal conductivity of the developed thin films reveals an increase in thermal conductivity from 2 W/m K to 5.8 W/m K for as grown and 40 min annealed samples respectively.     

Critical properties of superconducting Ba1−xKxFe2As2

Magnetisation and magneto-resistance measurements have been carried out on superconducting Ba_1?xK_xFe₂As₂ samples with x = 0.40 and 0.50. From high field magnetization hysteresis measurements carried out in fields up to 16 T at 4.2 K and 20 K, the critical current density has been evaluated using the Bean critical state model. The J_C determined from the high field data is >10⁴ A/cm² at 4.2 K and 5 T. The superconducting transitions were also measured resistively in increasing applied magnetic fields up to 12 T. From the variation of the T_C onset with applied field, dH_C2/dT at T_C was obtained to be ?7.708 T/K and ?5.57 T/K in the samples with x = 0.40 and 0.50.     

Thermoelectric power of CuCrxVySe4 p-type spinel semiconductors

Structural, electrical and magnetic measurements of polycrystalline CuCr_xV_ySe₄ spinels with x=1.79, 1.64 and 1.49 and y=0.08, 0.22 and 0.45, respectively, are presented. The compounds under study crystallize in regular system of a normal spinel type MgAl₂O₄ structure with the space group symmetry Fd3m. The chromium spins are coupled ferromagnetically and show both strong long- and short-range magnetic interactions evidenced by the large values of the Curie (T_C) and Curie–Weiss (θ_CW) temperatures, decreasing from T_C=407 K and θ_CW=415 K for y=0.08, via T_C=349 K and θ_CW=367 K for y=0.22 to T_C=283 K and θ_CW=293 K for y=0.45, respectively. In all the studied spinels a change of the electrical conductivity character from the semiconductive into the metallic one above 230 K was observed. A detailed thermoelectric power analysis showed a domination of diffusion thermopower component, maximum of phonon drag component at 230 K, a decrease of impurity component with increasing V content, as well as the weak magnon excitations at 40 K.     

Structural and magnetic properties of the double perovskite Sr2MnWO6

The nuclear and magnetic structure and the magnetic properties of the polycrystalline double perovskite Sr₂MnWO₆ have been studied. Rietveld analysis of neutron powder diffraction (NPD) data at T=295 K shows that the sample is tetragonal (space group P4₂/n, a=8.0119(4) Å, c=8.0141(8) Å). Some additional magnetic diffraction peaks were found in the NPD pattern at 10 K, which can be accounted for by antiferromagnetic ordering of spins at the Mn sites. The magnetic unit cell is doubled in all three unit axes directions (a=b=15.9984(8) Å, c=16.012(2) Å) and the manganese moments are coupled antiferromagnetically along the unit cell axes. The total magnetic moment of Mn²⁺ is found to be 2.27(7) μ_B. The antiferromagnetic behaviour was confirmed from magnetisation measurements. The transition from a paramagnetic to an antiferromagnetic state takes place at 13.0±0.1 K.     

Synthesis and characterization of La4Ni3−xCoxO10±δ (0.0 ≤ x ≤ 3.0, Δx = 0.2) for solid oxide fuel cell cathodes

The cobalt-doped lanthanum–nickel oxide system, La₄Ni_(3−x)Co_xO_10±δ (0.0 ≤ x ≤ 3.0, Δx = 0.2), was investigated as possible cathode materials for intermediate-temperature solid-oxide fuel cells. X-ray diffraction shows the presence of two structural phases in the series belonging to Bmab for 0.0 ≤ x ≤ 0.2, 0.8 ≤ x ≤ 2.0 and 2.6 ≤ x ≤ 3.0 and Fmmm for 0.4 ≤ x ≤ 0.6 and 2.2 ≤ x ≤ 2.4. All compositions are oxygen-deficient (δ < 0). Electrical conductivity measurements show a systematic decrease in the conductivity as cobalt content increases from x = 0.0 to 2.0, and reverses for x > 2.0. AC impedance measurements of the x = 0.4 composition in symmetrical cells with LSGM as an electrolyte show improved electrode performance over the parent nickelate La₄Ni₃O_9.78. Long-term thermal stability studies show the x = 0.4 composition to be more stable than the x = 3.0 phase after annealing at 1173 K in air for 1 week making this material a viable candidate for cathodes in solid oxide fuel cells.     

Effects of Zr impurity on microscopic behavior of Hf metal

Hf metal with ∼ 3 wt% Zr impurity has been reinvestigated by perturbed angular correlation (PAC) spectroscopy using a LaBr₃(Ce)–BaF₂ detector set up to understand the microscopic behavior of this metal with temperature. From present measurements, five quadrupole interaction frequencies have been found at room temperature where both pure hcp fraction (∼33%) with 12 nearest neighbor Hf surrounding the probe ¹⁸¹Hf atom and the probe–impurity fraction (∼33%) corresponding to 11 nearest neighbor Hf plus one dissimilar Zr atom are clearly distinguished. At room temperature, the results for quadrupole frequency and asymmetry parameter are found to be ω_Q=51.6(4) Mrad/s, η=0.20(4) for the impurity fraction and ω_Q=46.8(2) Mrad/s, η=0 for the pure fraction with values of frequency distribution width δ=0 for both components. At 77 K, only 1 NN Zr impurity (∼93%) and pure hcp (∼7%) components have been found with a value of δ ∼ 10% for the impurity fraction. A drastic change in microstructural configuration of Hf metal is observed at 473 K where the impurity fraction increases to ∼ 50% and the pure hcp fraction reduces to ∼ 15% with abrupt changes in quadrupole frequencies for both components. The pure fraction then increases with temperature and enhances to ∼50% at 973 K. In the temperature range 473–973 K, quadrupole frequencies for both components are found to decrease slowly with temperature. Using the Arrhenius relation, binding energy (B) for the probe–impurity pair and the entropy of formation are measured from temperature dependent fractions of probe–impurity and pure hcp in the temperature range 473–773 K. The three other minor components found at different temperatures are attributed to crystalline defects.     

Mixed conductivity and electrocatalytic performance of SrFeO3-δ–SrAl2O4 composite membranes

Oxygen-ionic and electronic transport in dense (SrFe)_1−x(SrAl₂)_xO_z composites, consisting of strontium-deficient Sr(Fe,Al)O_3-δ and SrAl₂O₄ phases, is determined by the properties of perovskite-like solid solution. Increasing the content of SrAl₂O₄, with a total conductivity as low as 5 × 10^− 7 −  10^− 5 S × cm^− 1 at 973–1273 K in air, results in the gradual decrease of the partial conductivities, but also enables the suppression of thermal expansion. Compared to single-phase SrFe_1−xAl_xO_3-δ, (SrFe)_1−x(SrAl₂)_xO_z composites exhibit enhanced thermomechanical properties, while the oxygen permeability of these materials has similar values. The composite membranes exhibit stable performance under air/(H₂–H₂O–N₂) and air/(CH₄–He) gradients at 973–1173 K. The oxidation of dry methane by oxygen permeating through (SrFe)_0.7(SrAl₂)_0.3O_z results in dominant total oxidation, suggesting the necessity to incorporate a reforming catalyst into the ceramic reactors for natural gas conversion.     

High coercivity Nd2(Fe,Co)14C-type ribbons prepared by melt spinning

Melt-spun Nd₁₃Dy₂Fe_77−xCo_xC₆B₂ (x=0, 5, 10, 15, 20) ribbons with a high coercivity more than 2 T have been obtained. It was found that the ribbons quenched at the optimum wheel speed 15 m/s (as-spun ribbons) mainly consist of ferromagnetic 2 : 14 : 1 phase and paramagnetic NdC₂ phase, and the ribbons spun at 25 m/s and subsequently annealed at 973 K for 15 min (as-annealed ribbons) are primarily composed of the magnetic 2 : 14 : 1 and 2 : 17 phases. The magnetization process of as-spun ribbons controlled by a pinning of the domain wall is different from that of as-annealed ribbons determined by a nucleation of the reverse domain. This significant difference originates possibly from the existence of paramagnetic NdC₂ phase acting as a pinning center in as-spun ribbons. In the as-annealed ribbons, the substitution of Co for Fe leads to increase of remanence (μ₀M_r), maximum energy product ((BH)_max) from 0.67 T, 9.7 MGOe for x=0 to 0.84 T, 14.4 MGOe for x=10, respectively. A coercivity of 2.74 T is obtained for as-quenched Nd₁₃Dy₂Fe_77−xCo_xC₆B₂ (x=0) ribbons.