Improvement of high-temperature oxidation resistance of TiAl-based alloy by sol–gel method

Lithium lanthanoid silicate, a high temperature lithium ion conducting solid electrolyte, synthesized by sol–gel method, has been characterized by TGA/DTA, XRD, FTIR and SEM. Conductivity was found to be 0.847 × 10⁻⁶ Ω⁻¹ cm⁻¹ at 750 °C and activation energy was 0.5 eV.     

Synthesis and characterization of doped LaCrO3 perovskite prepared by EDTA–citrate complexing method

The La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ (LSC) interconnect materials for solid oxide fuel cells (SOFCs) were synthesized by EDTA–citrate complexing method. Thermal decomposition behavior of the gel, phase formation and morphology of LSC powders were characterized by thermogravimetry/differential thermal (DSC/TG) analysis, X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. It appeared that lower pH value (pH 4.9) of the precursor solution resulted in a transient liquid phase, SrCrO₄, in the calcined LSC powder. The sintering characteristics, electrical conductivity and thermal expansion properties of sintered bars were investigated. La_0.85Sr_0.15Cr_0.95Ni_0.02Co_0.02O₃ prepared in the condition of pH 4.9 showed an electrical conductivity of 15.6 S cm⁻¹ at 800 °C and a thermal expansion coefficient (TEC) of 10.8 × 10⁻⁶ K⁻¹ (20–900 °C), which is suitable for use as interconnect materials for SOFCs.     

New low thermal expansion ceramics: Sintering and thermal behavior of Ln1/3Zr2(PO4)3-based composites

Materials with the general formula M_xZr₂(PO₄)₃ are known to possess low coefficients of thermal expansion (CTE). The present work investigates the thermal properties of new composite materials issued from the decomposition at high temperature of Ln_1/3Zr₂(PO₄)₃ (Ln=La, Gd). The decomposition process was studied and showed that the resulting powder was a LnPO₄, Zr₂P₂O₉ and ZrO₂ mixture. Composite materials made of that mixture were sintered and characterized. The effect of sintering aids such as ZnO was considered. Final densities of the composites were about 90% of theoretical density and these materials presented low CTE in the 10⁻⁶ °C⁻¹ range.     

Power factor of La1−xSrxFeO3 and LaFe1−yNiyO3

The electrical conductivity (σ), Seebeck coefficient (S), and power factor (σS²) of perovskite-type LaFeO₃, La_1−xSr_xFeO₃ [0.1 ≤ x ≤ 0.4] and LaFe_1−yNi_yO₃ [0.1 ≤ y ≤ 0.6] were investigated in the temperature range of 300–1100 K to explore their possibility as thermoelectric materials. The electrical conductivity of LaFeO₃ showed semiconducting behavior, and its Seebeck coefficient changed from positive to negative around 650 K with increasing temperature. The electrical conductivity of LaFeO₃ increased with the substitutions of Sr and Ni atoms, while its Seebeck coefficient decreased. The Seebeck coefficient of La_1−xSr_xFeO₃ was positive, whereas that of LaFe_1−yNi_yO₃ changed from positive to negative with increasing Ni content. The substitutions of Sr and Ni were effective in increasing the power factor of LaFeO₃; 0.0053 × 10⁻⁴ Wm⁻¹ K⁻² for LaFeO₃ (1050 K), 1.1 × 10⁻⁴ Wm⁻¹ K⁻² for La_1−xSr_xFeO₃ (x = 0.1 at 1100 K) and 0.63 × 10⁻⁴ Wm⁻¹ K⁻² for LaFe_1−yNi_yO₃ (y = 0.1 at 1100 K).     

Novel alkaline-free Er-doped fluorophosphate glasses for broadband optical fiber lasers and amplifiers

Two sets of Er³⁺-doped alkaline-free glass systems, MgF₂–BaF₂–Ba(PO₃)₂–Al(PO₃)₃ (MBBA) and Bi(PO₃)₃–Ba(PO₃)₂–BaF₂–MgF₂ (BBBM), have been prepared and investigated with the aim of using them as active media. Radiative lifetimes (τ_rad) and branching ratios (β) have been obtained for the excited states of Er³⁺. The absorption spectra were recorded to obtain the intensity parameters (Ω_t) which are found to be Ω₂ = 4.47 × 10⁻²⁰ cm², Ω₄ = 1.31 × 10⁻²⁰ cm², Ω₆ = 0.81 × 10⁻²⁰ cm² for the MBBA system and Ω₂ = 4.03 × 10⁻²⁰ cm², Ω₄ = 1.34 × 10⁻²⁰ cm², Ω₆ = 0.53 × 10⁻²⁰ for the BBBM system, respectively. The emission cross-section for the ⁴I_13/2 → ⁴I_15/2 transition is determined by the Fuchtbauer–Ladenburg method and found to be 2.35 × 10⁻²⁰ cm² and 3.54 × 10⁻²⁰ cm² for the MBBA and BBBM system, respectively. Comparison of the measured values to those of Er³⁺ transitions in other glass hosts suggests that our new glass systems are good candidates for broadband compact optical fiber and waveguide amplifier applications.     

Dielectric properties of sintered aluminum nitride

In the present work, the effects of sintering additives on dielectric loss tangent (tan δ) of AlN ceramics were explored. Different amounts of Y₂O₃ and Mg₃N₂ were respectively added as sintering additives to AlN powders, and pressureless-sintering was performed at 1900 °C for 2 h in a nitrogen flow atmosphere. The resulted AlN ceramics became denser due to the addition of Mg₃N₂, and nearly fully dense sample was obtained with a relative density of 0.998. tan δ decreased with increasing Mg₃N₂ amount and it was found to depend on the density of the AlN ceramic. The best tan δ value of 3.9 × 10⁻⁴ was obtained by adding 1 mol% of Y₂O₃ and Mg₃N₂ together.     

Sm0.5Sr0.5CoO3 cathode material from glycine-nitrate process: Formation, characterization, and application in LaGaO3-based solid oxide fuel cells

Cathode material Sm_0.5Sr_0.5CoO₃ (SSC) with perovskite structure for intermediate temperature solid oxide fuel cell was synthesized using glycine-nitrate process (GNP). The phase evolution and the properties of Sm_0.5Sr_0.5CoO₃ were investigated. The single cell performance was also tested using La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) as electrolyte and SSC as cathode. The results show that the formation of perovskite phase from synthesized precursor obtained by GNP begins at a calcining temperature of 600 °C. The single perovskite phase is formed completely after sintering at a temperature of 1000 °C. The phase formation temperature for SSC with complete single perovskite phase is from 1000 to 1100 °C. The SrSm₂O₄ phase appeared in the sample sintered at 1200 °C. It is also found that the sample sintered at 1200 °C has a higher conductivity. The electrical conductivity of sample is higher than 1000 S/cm at all temperature examined from 250 to 850 °C, and the highest conductivity reaches 2514 S/cm at 250 °C. The thermal expansion coefficient of sample SSC is 22.8 × 10⁻⁶ K⁻¹ from 30 to 1000 °C in air. The maximum output power density of LSGM electrolyte single cell attains 222 and 293 mW/cm² at 800 and 850 °C, respectively.     

Direct synthesis of La9.33Si6O26 ultrafine powder via sol–gel self-combustion method

Single phase La_9.33Si₆O₂₆ ultrafine powder, as a kind of highly activated precursor to prepare medium-to-low temperature electrolyte for solid oxide fuel cells (SOFCs), has been successfully synthesized via a non-aqueous sol–gel and self-combustion approach from the starting materials: lanthanum nitrate (La(NO₃)₃·6H₂O), citric acid, ethylene glycol (EG), tetraethyl orthosilicate (TEOS) and ammonium nitrate. The details of gel's self-combustion were investigated by DTA–TG and the structural characterization of as-synthesized powder from self-combustion was performed by XRD and SEM. The results show that La_9.33Si₆O₂₆ single phase of apatite-type crystal structure can be directly synthesized by sol–gel self-combustion method without further calcinations on the condition that the molar ratio (R) of NO₃⁻ to citric acid and ethylene glycol being 6:1. Such powders composed of well-dispersed particles with an average size of 200 nm and a specific surface area of 5.54 m²/g. It can be sintered to 90% of its theoretical density at 1500 °C for 10 h, about 200 °C lower than the sintering temperature for the powder derived from traditional solid reactions. The sintered material has a thermal expansion coefficient of 9.2 × 10⁻⁶ K⁻¹ between room temperature and 800 °C.     

Electrochemical properties of the MmNi3.55Mn0.4Al0.3Co0.4Fe0.35 compound

In this paper, the electrochemical properties of the MmNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy used as a negative electrode in Ni–MH accumulators, have been investigated by different electrochemical methods such as cyclic voltammetry, chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy. The experimental results indicate that the discharge capacity reaches a maximum value of 260 mAh g⁻¹ after 12 cycles and then decreases to about 200 mAh g⁻¹ after 70 cycles. The value of the mean diffusion coefficient D_H, determined by cyclic voltammetry, is about 3.44 × 10⁻⁹ cm² s⁻¹, whereas the charge transfer coefficient , determined by the same method, is about 0.5 which allows us to conclude that the electrochemical reaction is reversible. The hydrogen diffusion coefficients in this compound, corresponding to 10 and 100% of the charge state, determined by electrochemical impedance spectroscopy, are, respectively, equal to 4.15 × 10⁻⁹ cm² s⁻¹ ( phase) and 2.15 × 10⁻⁹ cm² s⁻¹ (β phase). These values are higher, for the phase and less, for the β phase, than the mean value determined by cyclic voltammetry. We assume that this is related to the number of interstitial sites susceptible to accept the hydrogen atom, which are more numerous in the phase than in the β phase. The chronoamperometry shows that the average size of the particles involved in the electrochemical reaction is about 12 μm.     

Preparation and bulk thermal expansion studies in M1−xCexSiO4 (M = Th, Zr) system, and stabilization of tetragonal ThSiO4

Two series of compositions with the general formula M_1−xCe_xSiO₄ (M = Th, Zr; x = 0.0–0.5; 1.0) were prepared by a standard solid state route and characterized by powder XRD. About 10 mol% of ceria could be dissolved in the lattice of ThSiO₄. A striking observation was the stabilization of tetragonal modification of ThSiO₄, which is metastable, by ceria substitution. There was no solubility of ceria in zircon (ZrSiO₄) lattice. The average linear thermal expansion coefficient (293–1123 K) of ZrSiO₄, ThSiO₄ and Th_0.9Ce_0.1SiO₄ are 4.65 × 10⁻⁶, 4.97 × 10⁻⁶ and 5.14 × 10⁻⁶ K⁻¹, respectively.     

Features of the HDDR process in R–Fe–B ferromagnetic alloys (R is a mixture of Nd, Pr, Ce, La, Dy and others)

Features of the conventional hydrogenation, disproportionation, desorption, recombination (HDDR) and solid-HDDR processes in some R–Fe–B (R is a mixture of Nd, Pr, Ce, La, Dy) ferromagnetic alloys were studied in the temperature range 20–990 °C and pressure range from 1×10⁻³ Pa to 0.1 MPa. This was carried out by means of differential thermal analysis (DTA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) methods. The hydride of the initial phase is formed by heating to 115 °C. The disproportionation of the alloys occurs in the temperature range from 320 to 800 °C. Φ-phase constitutes the base of the initial alloys. Among the disproportionation products, R-hydride, -Fe and two borides (Fe₂B and R_1.1Fe₄B₄) were revealed. The initial phase in all the alloys is recovered after heating in vacuum to a temperature of 990 °C. Full hydrogen desorption occurs in two temperature ranges with the peaks at 200–320 and 630–715 °C.     

Microstructure and thermoelectric properties of n-type Bi2Te2.85Se0.15 prepared by mechanical alloying and plasma activated sintering

Starting from elemental bismuth, tellurium and selenium powders, n-type Bi₂Te_2.85Se_0.15 solid solution with fine microstructure was prepared by mechanical alloying (MA) and plasma activated sintering (PAS) in the present work. The effect of PAS process on microstructure and thermoelectric properties of the sintered samples was investigated. The sintering temperature of PAS process (683 K) was 80–100 K lower than that of conventional hot pressing and the whole PAS process was also greatly shortened to about 30 min. A preferentially orientated microstructure with the basal planes (0 0 l) perpendicular to pressing direction was formed in the PASed sample and the maximum figure of merit (Z) at room temperature was 1.80 × 10⁻³ K⁻¹.     

Synthesis, crystal structure, oxygen stoichiometry, and electrical conductivity of La1−aCaaCr0.8Ti0.2O3−δ solid solutions

Series of perovskite-type compounds La_1−aCa_aCr_0.8Ti_0.2O_3−δ (a=0–1.0) were synthesized by the ceramic technique in air (final heating 1350 °C). The crystal structure of the compounds after cooling in air to room temperature was characterized as orthorhombic in space group Pbnm. Analysis of the lattice constants shows a noticeable decrease with increasing Ca content. All compounds prepared were stable in air and in a stream of Ar/1 Pa O₂ at 20–1400 °C, as also in Ar/5% H₂ (pH₂O/pH₂=0.01) at 850–1000 °C. Oxygen stoichiometry and electrical conductivity of the solid solutions with a=0.0–1.0 are investigated. Increasing Ca contents decrease the stability of the oxides in respect to the thermal dissociation of oxygen. All compounds are p-type semiconductors in the temperature range 20–1000 °C at oxygen partial pressures of 10⁻¹⁵ to 0.21×10⁵ Pa. A maximum conductivity of about 30 S/cm in air at 1000 °C is observed for the composition with a=0.6 corresponding to a ratio of Cr³⁺/Cr⁴⁺=1 at an oxygen stoichiometry near 3.0, and oxidation states of La, Ca, Ti, and O ions of 3+, 2+, 4+, and 2−, respectively.     

Selected corrosion behaviors of a Cu0.5NiAlCoCrFeSi bulk glassy alloy in 288 °C high-purity water

Selected corrosion behaviors of a Cu_0.5NiAlCoCrFeSi bulk glassy alloy like electrochemical corrosion potential (ECP), potentiodynamic polarization, and weight loss were investigated in 288 °C high-purity water. The change of ECP with dissolved oxygen showed a sigmoid curve. The Cu_0.5NiAlCoCrFeSi alloy exhibited a wide passive region and the passive current density was 2 × 10⁻⁴ A/cm² in deaerated 288 °C water containing 0.01 N sodium sulfate. A low weight loss of 4.5 μg/mm² was found for the Cu_0.5NiAlCoCrFeSi alloy after immersion in deaerated 288 °C water for 12 weeks.     

Achieving tensile superplasticity in 8 mol% Y2O3 cubic stabilized ZrO2 through the addition of intergranular silica

The addition of 5 wt.% SiO₂, a viscous second phase, to 8 mol% Y₂O₃ cubic stabilized ZrO₂ (8Y-CSZ) made superplastic 8Y-CSZ. This material had a fine grain size of 0.4 μm and exhibited deformations in tension as large as 520% at 1430 °C with a strain rate of 1.0 × 10⁻⁴ s⁻¹.     

Superplastic behavior of a 7055 aluminum alloy

It is shown that a high strength 7055 aluminum alloy with partially recrystallized initial structure exhibits superplastic behavior in the temperature interval 400–490 °C within a wide strain rate range from 8.3×10⁻⁵ to 3.3×10⁻² s⁻¹. Maximum total elongation of about 960% and strain rate sensitivity coefficient, m, of 0.6 were obtained at a temperature of 450 °C and a strain rate of 3.3×10⁻⁴ s⁻¹.     

The ternary system: silicon–titanium–uranium

Phase equilibria in the system Si–Ti–U were established at 1000 °C by optical microscopy, EMPA and X-ray diffraction. Two ternary compounds were observed and were characterised by X-ray powder data refinement: (1) stoichiometric U₂Ti₃Si₄ (U₂Mo₃Si₄-type) with a small homogeneity region of about 3 at.% exchange U/Ti and (2) U_2−xTi_3+xSi₄ (Zr₅Si₄-type) extending at 1000 °C for 0.7<x<1.3. Mutual solubility of U-silicides and Ti-silicides was found to be below about 1 at.%. The Ti,U-rich part of the diagram was also investigated at 850 °C establishing the tie-lines to the low temperature compounds U₂Ti and U₃Si. U₂Ti₃Si₄ is weakly paramagnetic following a Curie–Weiss law above 50 K with μ_eff.=2.67 μ_B/U, Θ_P=−150 K and χ₀=1.45×10⁻³ emu/mol (18.2×10⁻⁹ m³/mol).     

Electrochemical investigation of the iron-containing and no iron-containing AB5-type negative electrodes

The electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x (x = 0, 0.15, 0.55, 0.75) intermetallic compounds has been studied and presented [C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, Int. J. Hydrogen Energy 29 (2004) 307–311; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 360 (2003) 266–271; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 384 (2004) 249–253]. It has been deduced that the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound has interesting electrochemical properties. In this paper we present the electrochemical study of LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound properties compared with the parent LaNi_3.55Mn_0.4Al_0.3Co_0.75 compound. Several techniques, such as, the chronopotentiometry, the constant potential discharge (CPD), the cyclic voltammetry (CV) and the linear polarization (LP) were applied to characterize these electrochemical properties. The electrochemical discharge capacity of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 alloy increases to reach 294 mAh g⁻¹ after few cycles only (five cycles). However, the activation of the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy takes more than 20 cycles to be achieved and the obtained maximum discharge capacity is 194 mAh g⁻¹. The hydrogen diffusion coefficient D_H was determined by constant potential discharge and cyclic voltammetry techniques. The obtained values of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compounds are 6.29 × 10⁻¹¹ and 7.62 × 10⁻¹¹, and 2 × 10⁻⁸ and 7.5 × 10⁻⁸ cm² s⁻¹ by CPD and CV techniques, respectively. The exchange current density values, determined by a linear polarization technique, are 44 and 27 mA g⁻¹, respectively, for LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloys.     

Influence of Al- and Cu-doping on the thermodynamic properties of the LaNiIn–H system

The Pressure–Composition–Temperature (P–C–T) relations for the LaNiIn, LaNi_0.95Cu_0.05In and LaNiIn_0.98Al_0.02–H systems were measured by a volumetric Sieverts’ method at 398–423 K. All isotherms show plateau pressure regions indicating equilibria between two hydride phases. The replacements of Ni by Cu and In by Al affect the P–C–T diagrams, stability of the hydrides, homogeneity regions of the hydrides formed, slope of the isotherms and critical temperatures of the β–γ transition. In addition, the Cu-doping induces a significant hysteresis between the hydrogen absorption and desorption processes. The relative partial molar thermodynamic properties for the studied systems are: ΔH_H = −34.6 ± 2.1 kJ (mol_H)⁻¹, ΔS_H = −70.7 ± 3.6 J (K·mol_H)⁻¹ for LaNiIn–H; ΔH_H = −34.1 ± 0.5 kJ (mol_H)⁻¹, ΔS_H = −74.9 ± 1.0 J (K·mol_H)⁻¹ for LaNi_0.95Cu_0.05In–H; ΔH_H = −33.2 ± 0.8 kJ (mol_H)⁻¹, ΔS_H = −68.3 ± 1.2 J(K·mol_H)⁻¹ for LaNiIn_0.98Al_0.02–H.