Sintering kinetics and oxide ion conduction in Sr-doped apatite-type lanthanum silicates,La9Sr1Si6O26.5

These last past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cells (SOFCs) down to about 700 °C.Apatite materials (La_10 ? xSr_xSi₆O_27?x/2) are attractive candidates for solid electrolytes, with a high ionic conductivity at these intermediate temperatures. An apatite powder (x = 1) with a 0.75 µm mean particle size, produced by solid state reaction, was tape cast to obtain green sheets with a thickness of about 260 µm.On one hand, the densification mechanism of the apatite ceramic during the intermediate solid state sintering has been approached. It appeared from the kinetical tests performed under isothermal conditions between 1250 and 1550 °C, that densification could be controlled by the diffusion at grain boundaries of the rare-earth element, La, with an activation energy of 470 kJ/mol.On the other hand, conductivity measurements were performed on apatite samples sintered at 1400 and 1500 °C. The ionic conductivity was mainly sensitive to the presence of secondary phases at 1400 °C. The ionic conductivity of the apatite sintered at 1500 °C (mean grain size = 3.9 µm) is equal to 1.2 × 10^? 2 S/cm at 700 °C.     

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.     

Effect of strontium addition on europium-doped ceria properties

Nanopowders of composition Ce_0.9(Eu_1 ? xSr_x)_0.1O_2 ? δ (x = 0, 0.1, 0.3, 0.5, and 0.7) were prepared by the Pechini method. The microstructure and properties of powders and sintered ceramics are discussed in this paper. X-ray diffraction (XRD) and Raman spectroscopy revealed that all powders calcined at 550 °C were single phase, with the cubic fluorite-type structure. The good sintering properties of the synthesized nanopowders allowed us to obtain dense ceramics (> 96% theoretical density). Dense ceramics with density higher than 96% of the theoretical value were obtained without the need of sintering aid. The morphology of the sintered ceramics was evidenced by scanning electron microscopy (SEM). The ionic conductivities of doped and co-doped ceria ceramics were investigated as a function of temperature by using AC impedance spectroscopy in the temperature range 250–800 °C. Impedance spectra indicate a significant diminution of grain boundary resistance after partial substitution of Eu with Sr in europia-doped ceria sample, especially in the low and intermediate-temperature range. The best conductivity was evidenced for the Ce_0.9Eu_0.09Sr_0.01O_2 ? δ composition.     

Electrical conductivity of fully densified nano CaZr0.90In0.10O3 − δ ceramics prepared by a water-based gel precipitation method

Water-based gel precipitation method was first applied to synthesize high purity nano CaZr_0.90In_0.10O_3 ? δ powders suitable for fabricating dense ceramics at lower temperature. By using CaCO₃, Zr(NO₃)₄ and In(NO₃)₃ as raw materials, PEG as dispersant, CaZr_0.90In_0.10O_3 ? δ with an average particle size of about 40 nm was obtained at 850 °C, which was nearly 350 °C lower than that of traditional solid-state reaction method. Fully densified ceramics with an average grain size of 200–300 nm were obtained at 1350 °C, a temperature about 250 °C lower than that of traditional sintering techniques. Experimental results showed that the flexure stress, total, bulk and grain boundary protonic conductivities of the ceramics were more favorable than those of the ceramics fabricated at 1500 °C and 1600 °C from the powders synthesized by solid-state reaction method.     

Low-temperature preparation and properties of ceramics with composition (1−x)CaTiO3−xPbF2−xLiF

Fluorinated ceramics with initial composition (1−x)CaTiO₃+xPbF₂+xLiF were sintered at 950 °C. The X-ray diffraction (XRD) patterns of the samples showed the formation of a novel solid solution in the initial composition range 0⩽x⩽0.125. SEM observations were performed on fractured ceramics and DSC analyses were carried out from room temperature up to 600 °C. Three second-order phase transitions were detected for all the samples. Capacitors were prepared from the pre-sintered ceramics then dielectric measurements were performed as a function of temperature in the frequency range 10²–4×10⁷ Hz. The ε′_r−T curves exhibit the profile of dielectrics for class I capacitors, however the values of tan δ are too high (tan δ⩾1%).     

Electrical conductivity and thermal expansion of the oxy-cuspidine Gd4Al2O9 substituted with Ca and Sr

The series of Gd_4 ? xM_xAl₂O_9 ? x/2 (M = Ca, Sr) with x = 0, 0.01, 0.05, 0.10 and 0.25 was prepared by the citrate complexation method. Both Gd_4 ? xCa_xAl₂O_9 ? x/2 and Gd_4 ? xSr_xAl₂O_9 ? x/2 show the monoclinic cuspidine structure with space group of P2₁/c up to 0.05–0.1 and 0.01–0.05 mol for Ca and Sr, respectively. Beyond the substitution limit of Gd₄Al₂O₉, GdAlO₃ and SrGd₂Al₂O₇ appear as additional phases. The highest electrical conductivity obtained at 900 °C yielded σ = 1.49 × 10^? 4 S/cm for Gd_3.95Ca_0.05Al₂O_8.98. In comparison, the conductivity of pure Gd₄Al₂O₉ was σ = 1.73 × 10^? 5 S/cm. The conductivities determined are in a similar range as those of other cuspidine materials investigated previously. The thermal expansion coefficient of Gd₄Al₂O₉ at 1000 °C was 7.4 × 10^? 6 K^? 1. The phase transition between 1100 and 1200 °C reported earlier changes with increasing substitution of Ca and Sr.     

Synthesis and electrical transport properties of Lu2+xTi2−xO7−x/2 oxide-ion conductors

The Lu_2+xTi_2−xO_7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu₂O₃) nanoceramics with partly disordered pyrochlore-type structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have oxide-ion conductivity in the interval of 1.0 × 10^− 3 – 2.5 × 10^− 3 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO₂/Y₂O₃ ceramics. The conductivity of Lu_2+xTi_2−xO_7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly stoichiometric Lu_2+xTi_2−xO_7−x/2 (x = 0.096; 35.5 mol% Lu₂O₃) material containing ∼ 4.8 at.% Lu_Ti anti-site defects.     

Conductivity of SnP2O7 and In-doped SnP2O7 prepared by an aqueous solution method

SnP₂O₇ and In-doped SnP₂O₇ have been prepared by an aqueous solution method using (NH₄)₂HPO₄ as phosphorous source. It was found that the solid solution limit in Sn_1 ? xIn_x(P₂O₇)_1 ? δ was at least x = 0.12. All pyrophosphates in the Sn_1 ? xIn_x(P₂O₇)_1 ? δ (x ≤ 0.12) series exhibit 3 × 3 × 3 superlattice structures. The conductivities of Sn_0.92In_0.08(P₂O₇)_1 ? δ in air are 6.5 × 10^? 6 and 8.0 × 10^? 9 S/cm at 900 and 400 °C, respectively, when prepared by an aqueous solution method and annealed at 1000 °C. The conductivity of undoped SnP₂O₇ is slightly lower. However, it was also found that the low-temperature conductivities of pyrophosphates annealed only at 650 °C are several orders of magnitude higher than those annealed at 1000 °C, which could be related to a trace amount of an amorphous secondary phase. The peak conductivity was in this case observed at around 250 °C, which is the same temperature as previously observed in In-doped SnP₂O₇ although the conductivity is still three orders of magnitude lower in the present study. These differences can be related to large differences in particle size and morphology, and all in all, the conductivities of SnP₂O₇-based materials are very sensitive to the synthetic history.     

Densification and microstructure of lead zirconate titanate ceramics fabricated from a triol sol–gel powder

Lead zirconate titanate (PZT) nano-powder was prepared by a triol sol–gel process. X-ray diffraction and transmission electron microscopy results showed that as-synthesized amorphous powder started to crystallize at the calcination temperature above 500 °C. The crystalline powder was formed into pellets and sintered at temperatures between 900 and 1300 °C. Co-existence of tetragonal and rhombohedral phase was observed in all ceramics. Microstructural investigation of PZT ceramics showed that uniform grain size distribution with average grain size of ∼0.8–2.5 μm were received with sintering temperature up to 1200 °C. Further increasing the temperature caused abnormal grain growth with the grain as large as 13.5 μm. An attempt to optimize densification with uniform grain size distribution was also performed by varying heating rate and holding time during sintering. It was found that dense (∼97%) sol–gel derived PZT ceramic with uniform microstructure was achieved at 1100 °C with a heating rate of 5 °C min⁻¹ and 6 h dwell time.     

Structural and electrical properties of tellurovanadate glasses containing Li2O

Glassy materials are promising intercalation compounds, due to their open network structure and absence of grain boundaries. Some glasses containing alkali ions and a high concentration of transition metal ions can present mixed ionic-electronic conductivity and are therefore potential candidates for application as cathode material in Li-ion batteries. The present work is devoted to the ternary system xLi₂O–(1 − x)[0.3V₂O₅–0.7TeO₂] with 0 ≤ x ≤ 0.4. These compounds were prepared by heat treatment in air at 800 °C followed by traditional quenching. Raman spectroscopy and ⁵¹V nuclear magnetic resonance measurements were performed in order to highlight the structural short range order modifications induced by the introduction of the Li₂O network modifier. These structural effects can be related to the electrical behaviour, as studied by complex impedance spectroscopy measurements.     

The effect of cation nonstoichiometry on the electrical conductivity of acceptor-doped CaZrO3

The electrical properties of acceptor-doped Ca_1−xZr_0.99M_0.01O_3−δ (M = Mg²⁺, In³⁺) systems were investigated as a function of cation nonstoichiometry (0 ≤ x ≤ 0.05). The characterization was carried out using the impedance spectroscopy between 550 °C and 1100 °C in dry air. The contributions of the grain and grain boundary conductivity to the total conductivity were obtained from the impedance data. When the Ca deficiency (x) increased, the total conductivity rapidly decreased with the corresponding increase in activation energy. Although the grain conductivity increased slightly with increasing x, the total conductivity is mostly determined by the highly resistive grain boundary. With varying x, the activation energy of total conductivity showed the percolation behavior. The percolation threshold values vary according to the doped species. It may be due to the difference in concentration of oxygen vacancies of the specimens.     

An oxygen permeable membrane La0.8Sr0.2(Ga0.8Mg0.2)1 − xCrxO3 − δ for a reduced atmosphere

Mixed electron hole and oxide ion conducting perovskite-type oxides, La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ (0 ≤ x ≤ 1.0)_, were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ increases with increasing x. The oxygen permeation flux across the La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10^? 7 mol^? 1 cm^? 2 at 1100 °C in a oxygen activity gradient of air/10^? 2 Pa is observed in La_0.8Sr_0.2(Ga_0.8Mg_0.2)_0.6Cr_0.4O_3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10^? 10 Pa at 1000 °C.     

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.     

Superconductivity in bulk T′-(La,Sm)2CuO4 prepared via a molten alkaline hydroxide route

We have synthesized La_2?xSm_xCuO₄ (0 ? x ? 2.0) with the Nd₂CuO₄ structure via a molten alkaline hydroxide route at temperatures as low as 400–480 °C. After reduction heat treatment in vacuum at 600–750 °C for removal of excess oxygen atoms at the interstitial apical site, superconductivity with T_c = 20–24 K was observed in the samples with x = 0.05–1.0. The superconducting volume fraction is nearly 100% for x = 0.3–0.7. Our results demonstrate that La_2?xSm_xCuO₄ with no nominal carrier doping is a bulk superconductor.     

Dielectric,optical and structural properties of Bi4V2−xSrxO11−δ (0.05≤x≤0.20)

Composition Bi₄V_2−xSr_xO_11−δ (0.05≤x≤0.20) is synthesized by melt quench technique followed by heat treatment at 800 °C for 12 h. These compounds are characterised by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, impedance spectroscopy and scanning electron microscopy. X-ray diffraction patterns of all the samples show γ-phase stabilization at room temperature except x=0.05 heat treated sample. The optical band gap of all the samples is observed in semiconducting range. The lowest and the highest optical band gap is 2.39 eV and 2.57 eV for x=0.10 heat treated and x=0.20 quenched samples, respectively. The highest value of dielectric constant is obtained ~10⁷ with very low dielectric loss for x=0.15 and 0.20 samples at ~350 °C and below 10 Hz. The grain size increases with dopant concentration leads to increase the dielectric constant.     

Field-assisted sustainable O− ion emission from fluorine-substituted 12CaO·7Al2O3 with improved thermal stability

We examined the electric field-assisted thermionic emission of atomic oxygen radical anion (O^?) in a vacuum from fluorine-substituted derivatives of 12CaO·7Al₂O₃ (C12A7) with a composition of (12 ? x)CaO·7Al₂O₃·xCaF₂ (0 ≤ x ≤ 0.8). Unsubstituted C12A7 easily decomposed into 5CaO?3Al₂O₃ (C5A3) and 3CaO?Al₂O₃ (C3A) above 830 °C during the emission experiment in a vacuum. The decomposition temperature range became narrower as the amount of F^? ion substitution increased, e.g. the sample with x = 0.4 kept a single phase after the emission experiment at 900 °C. The emitted anionic species from the x = 0.4 sample were dominated by O^? ions (～ 92%) together with a small amount of O₂^? ions (～ 4%) and F^? ions (～ 4%). The absence of an O₂ gas supply to the opposite side of the emission surface led to a nearly steady co-emission of O^? ions and electrons with a ratio of < 1/1. The O₂ gas supply markedly enhanced the O^? ion emission, and suppressed the electron emission. A sustainable and high-purity O^? ion emission with a current density of 11 nA cm^? 2 was achieved at 830 °C with the supply of 40 Pa O₂ gas. The similarity in these emission features to the unsubstituted C12A7, together with the improved thermal stability demonstrates that the F^? ion-substituted C12A7 is a promising material for higher intensity O^? ion emission at higher temperatures.     

Dielectric,ferroelectric and piezoelectric properties of (1−x)[K0.5Na0.5NbO3]−x[LiSbO3] ceramics

Lead-free (1?x)[K_0.5Na_0.5NbO₃]?x[LiSbO₃] (x=0, 0.04, 0.05 and 0.06)/(KNN-LS) ceramics were prepared by conventional solid-state reaction route (CSSR). For dense morphology pure KNN ceramic was sintered at 1120 °C and LS modified KNN ceramics were sintered at 1080 °C for 4 h, respectively. The structural study at room temperature (RT) revealed the transformation of pure orthorhombic to tetragonal structure with the increase in LS content in KNN-LS ceramics. Temperature dependent dielectric study confirmed the increase of diffuse phase transition nature with the increase in LS content in KNN-LS ceramics. The presence of orthorhombic to tetragonal (T_O?T) polymorphic phase transition temperature (PPT) ～43 °C confirmed the presence of two ferroelectric (orthorhombic and tetragonal) phases in 0.95KNN-0.05LS ceramics at RT. 0.95KNN-0.05LS ceramics showed better ferroelectric and piezoelectric properties i.e., remnant polarization (P_r)～18.7 μC/cm², coercive field (E_c)～11.8 kV/cm, piezoelectric coefficient (d₃₃)～215 pC/N, coupling coefficient (k_p)～0.415 and remnant strain ～0.07% were obtained.     

Characterization of Laves phase in Crofer 22 H stainless steel

This study investigated the effect of annealing temperature on the precipitation behavior of Crofer^® 22 H at 600 °C, 700 °C, and 800 °C. The grain size distribution, precipitate phase identification, and microstructure were analyzed using electron backscatter diffraction (EBSD) and energy dispersive X-ray spectroscopy (EDS). The morphology of Laves phase (Fe,Cr,Si)₂(Nb,W) precipitates having the Cr₂Nb structure changed from strip-like to needle-shaped as the annealing temperature was increased. The precipitates of the Laves phase also shifted from the grain boundaries to the grain interiors when the temperature was increased. However, the average grain size (150 μm) of the ferritic matrix did not significantly change at 600 °C, 700 °C, and 800 °C for 10 h.     

Tuneability of Sm(1 − x)CexFeO3 ± λ perovskites: Thermal stability and electrical conductivity

Trimetallic perovskite oxides, Sm_(1 ? x)Ce_xFeO_3 ± λ (x = 0–0.05), were prepared by thermal decomposition of amorphous citrate precursors followed by calcinations. The material properties of the substituted perovskites were characterized by X-ray diffraction (XRD), X-ray florescence spectroscopy (XRF), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The doped materials exhibited a single perovskite phase in air up to 1350 °C and have specific surface areas in the range of 2.696–8.665 m²/g. In reducing atmosphere (5%v/vH₂/N₂), the unsubstituted perovskite (x = 0) decomposed into two phases while the ceria stabilized materials (x = 0.01, x = 0.03, x = 0.05) remained in a single phase as revealed by XRD analysis. Their conductivities were measured by the four point probe method in air and in dilute hydrogen (5%v/vH₂/N₂) separately. The ceria substituted materials show increased stability versus reduction and phase separation for a wide temperature range (up to 1000 °C). Although undoped SmFeO₃ has higher conductivity under oxidizing conditions than ceria doped SmFeO₃ due its p-type nature, the situation is reversed under reducing conditions. The ceria substituted perovskites (Sm_(1 ? x)Ce_xFeO_3 ± λ, x = 0–0.05) showed higher conductivity in reducing than in oxidizing conditions, suggesting that ceria doping at the A-site has changed the SmFeO₃ from p-type to n-type semi-conducting behavior.     

Ultra-fast grain boundary diffusion and its contribution to surface segregation on a martensitic steel. Experiments and modeling

Phosphorus surface segregation was measured by Auger Electron Spectroscopy on a 17-4 PH martensitic stainless steel at 450, 550 and 600 °C. Surface segregation was shown to be much faster than expected which was attributed to a high contribution of phosphorus diffusion along the former austenitic grain boundaries. A model of surface segregation was developed following the Darken–du Plessis approach and taking account of both bulk and grain boundary solute diffusion. The phosphorus grain boundary diffusion coefficient in 17-4 PH was estimated: D_GB^< = 6.2 10⁴ exp(? 157 kJ mol^? 1/RT)cm² s^? 1. It is found to be more than three orders of magnitude higher in 17-4 PH steel than in α-iron.