Influence of processing on stability,microstructure and thermoelectric properties of Ca3Co4 − xO9 + δ

Due to high figure of merit, Ca₃Co_4 ? xO_9 + δ (CCO) has potential as p-type material for high-temperature thermoelectrics. Here, the influence of processing including solid state sintering, spark plasma sintering and post-calcination on stability, microstructure and thermoelectric properties is reported. By a new post-calcination approach, single-phase materials were obtained from precursors to final dense ceramics in one step. The highest zT of 0.11 was recorded at 800 °C for CCO with 98 and 72% relative densities. In situ high-temperature X-ray diffraction in air and oxygen revealed a higher stability of CCO in oxygen (～970 °C) than in air (～930 °C), with formation of Ca₃Co₂O₆ which also showed high stability in oxygen, even at 1125 °C. Since achievement of phase pure high density CCO by post-calcination method in air is challenging, the phase stability of CCO in oxygen is important for understanding and further improvement of the method.     

Shape Factor Effect on Inclusion Sedimentation in Aluminum Melts

Metallurgical and Materials Transactions B - The quality requirements of aluminum products are steadily increasing, and the presence of non-metallic inclusions have a large impact on the quality of...     

Kinetic Energy Approach to Dissolving Axisymmetric Multiphase Plumes

A phenomenological kinetic energy theory of buoyant axisymmetric multiphase plumes is constructed, with particular attention to the modeling of the dispersed phase. The dissolution is treated by means of the Ranz-Marshall equation involving a mass-transfer coefficient dependent on the plume properties. The model is compared with various experiments, yielding satisfactory agreement. A central ingredient in the model is the turbulent correlation parameter I, playing a role analogous to the conventional entrainment coefficient α. We use experimental data to suggest a relationship between I, the initial gas flux at the source, and the depth of the gas release.     

Template-assisted synthesis of PbTiO3 nanotubes

Nanotubes of ferroelectric lead titanate (PbTiO₃) have been made by a template-assisted method. An equimolar Pb–Ti sol was dropped onto porous alumina membranes and penetrated into the channels of the template. Single-phase PbTiO₃ perovskite nanotubes were obtained by annealing at 700 °C for 6 h. The nanotubes had diameters of 200–400 nm with a wall thickness of approximately 20 nm. Excess PbO or annealing in a Pb-containing atmosphere was not necessary in order to achieve single-phase PbTiO₃ nanotubes. The influence of the heating procedure and the sol concentration is discussed.     

Sintering of LaFeO3 Ceramics

The sintering of LaFeO₃ has been studied in the temperature interval 1100–1600°C in air. The effect of cation nonstoichiometry on densification, microstructure, and phase composition is emphasized. La₂O₃ was observed to inhibit both sintering and grain growth. In Fe-excess materials, exaggerated grain growth occurred, particularly above 1430°C, where a liquid phase was formed. Postsintering swelling was observed in Fe-excess materials above 1430°C. The swelling mechanism is related to phase equilibria, which are reductive in nature and lead to the evolution of oxygen gas. The density in La-excess materials remains high up to 1600°C, but the ceramics might disintegrate in air.     

Sintering behaviour of La1−xSrxFeO3−δ mixed conductors

The sintering properties of La_1−xSr_xFeO_3−δ (x = 0.1, 0.25) mixed conductors have been investigated with particular emphasis on the effect of secondary phases due to cation non-stoichiometry (±5 mol% La excess and deficiency). Secondary phases, located at grain boundaries in cation non-stoichiometric materials, increased the sintering temperature compared to single-phase materials. Extensive swelling in final stage of sintering was observed in all materials, which resulted in micro-porous materials. The swelling was most pronounced in the phase pure and two-phase materials due to La-deficiency, while refractory secondary phases in La-excess materials inhibited both sintering, grain growth and swelling. In La-deficient materials, formation of molten secondary phases resulted in rapid swelling due to viscous flow. The present findings demonstrated the importance of controlling sintering temperature and time, as well as careful control of the cation stoichiometry of La_1−xSr_xFeO_3−δ in order to achieve fully dense and homogenous La_1−xSr_xFeO_3−δ ceramics.     

High-Temperature Creep Behavior of Mixed Conducting La0.5Sr0.5Fe1−xCoxO3-δ (0.5≤x≤1) Materials

Steady-state compressive creep rate of La_0.5Sr_0.5Fe_0.5Co_0.5O_3−δ (LSFC) and La_0.5Sr_0.5CoO_3−δ (LSC) is reported in the temperature region 900°–1050°C and stress range 5–28 MPa. The stress exponents for the two materials were 1.71±0.18 and 1.24±0.15, respectively. The activation energy for creep was considerably higher for LSC (619±56 kJ/mol) than for LSFC (392±28 kJ/mol). The grain size exponent for LSC was 1.28±0.14. Considerably higher creep rates were observed for both materials in N₂ compared with air. Relaxation by creep of chemical-induced stresses in oxygen-permeable membranes is addressed, especially at low partial pressure of oxygen.     

Surface Diffusion of Oxygen Transport Membrane Materials Studied by Grain‐Boundary Grooving

Mass transport mechanism responsible for grain‐boundary grooving during thermal annealing of polished ceramics of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ (BSCF) and La₂NiO_4+δ (LN) was revealed by atomic force microscopy. Surface diffusion mechanism was confirmed for both materials by the evolution of the grain‐boundary width (w) with annealing time (t), and the surface diffusion coefficient was determined from the slope of w versus t^1/4 following the theory by Mullins. An Arrhenius temperature dependence of the surface diffusion was observed, and the activation energy was determined to be 220 ± 30 and 450 ± 30 kJ/mol, respectively, for BSCF and LN. The surface diffusion data are discussed with respect to similar data for other oxide materials and cation and oxygen anion diffusion in BSCF and LN. Finally, the dihedral angle for both LN and BSCF was determined, and these are typical in the range reported for other oxide materials.     

Effect of CO2 Exposure on the Chemical Stability and Mechanical Properties of BaZrO3‐Ceramics

The reactivity of BaZrO₃ with CO₂ has been addressed as one of the major challenges with BaZrO₃‐based electrolytes in protonic ceramic fuel cells. Here, we present a study of the effect of CO₂ exposure on BaZrO₃‐materials at elevated temperatures. Dense BaZr_1?xY_xO_3?x/2 (x = 0, 0.05, 0.1, 0.2) and BaCe_0.2Zr_0.7Y_0.1O_2.95 ceramics were prepared by sintering of powder prepared by spray pyrolysis. The Vickers indentation method was used to determine the hardness and estimate the fracture toughness of pristine materials as well as the corresponding materials exposed to CO₂. Formation of BaCO₃ on the surface of exposed ceramics was confirmed by X‐ray diffraction and electron microcopy. The reaction resulted in formation of Ba‐deficient perovskite at the exposed surface. The reaction with CO₂ was most pronounced at 650°C compared to the other temperatures applied in the study. The reactivity was also shown to depend on the Y‐content and the grain size and was most pronounced for BaZr_0.9Y_0.1O_2.95. The reaction with CO₂ was observed to have a profound effect on the fracture toughness of the ceramics, demonstrating a depression of the mechanical stability of the materials. The results are discussed with respect to the chemical and mechanical stability of BaZrO₃ materials, with particular emphasis on the composition and grain size.