Molecular dynamics simulations of oxygen diffusion in GdBaCo2O5.5

International audienceThe mechanisms of oxygen diffusion in GdBaCo2O5.5 compound are investigated by molecular dynamics simulations. The results confirm that diffusion is mainly bidimensional with oxygen moving in the a,b plane while diffusion along the c axis is much more difficult. Between 1000 and 1600 K, the activation energy for diffusion is about 0.6 eV, close to experimental values. Going deeper inside the oxygen diffusion mechanism, we see that this diffusion occurs mainly in the cobalt planes while most of the oxygen vacancies are kept in the Gd planes. Analysis of oxygen motions show that Gd planes can be seen as source-sink for the oxygen vacancies rather than as fast pathways

Thermodynamics of hydration and oxidation in the proton conductor Gd-doped barium cerate from density functional theory calculations

International audienceHydration and oxidation of gadolinium-doped barium cerate, a system with highly promising properties when used as electrolyte for protonic ceramic fuel cells, are investigated by means of density functional calculations. The energy landscape of oxygen vacancies and interstitial protons in this strongly distorted orthorhombic perovskite is computed. Although the most stable sites for protons are found in the close vicinity of the dopant, the picture of a very complex energy landscape emerges, in which some sites far away from Gd are found more stable than other ones in its close vicinity, due to the highly distorted geometry of the hostmaterials. The fully hydrated phase can be approximated by a structure with 16 local minima. Both hydration (water incorporation) and oxidation (oxygen incorporation) are found to be exothermic processeswith reaction enthalpies of−1.34 eV/H2Omolecule and −0.70 eV/O atom, respectively. The hole polaron resulting from the exothermic incorporation of oxygen is found localized on oxygens around the dopant (small polaron) and carries a spin magnetic moment. Finally, the competition between hydration and oxidation is studied and discussed as a function of oxygen and water partial pressures

Improving the functional properties of (K0.5Na0.5)NbO3 piezoceramics by acceptor doping

ZrO2 and TiO2 modified lead-free (K0.5Na0.5)NbO3 (KNN) piezoelectric ceramics are prepared by a conventional solid-state reaction. The effect of acceptor doping on structural and functional properties is investigated. A decrease in the Curie temperature and an increase in the dielectric constant values are observed when doping. More interestingly, an increase in the coercive field E-c and remanent polarization P-r is observed. The piezoelectric properties are greatly increased when doping with small concentrations dopants. ZrO2 doped ceramic exhibits good piezoelectric properties with piezoelectric coefficient d(33) = 134 pC/N and electromechanical coupling factor k(p) = 35%. It is verified that nonlinearity is significantly reduced. Thus, the creation of complex defects capable of pinning the domain wall motion is enhanced with doping, probably due to the formation of oxygen vacancies. These results strongly suggest that compositional engineering using low concentrations of acceptor doping is a good means of improving the functional properties of KNN lead-free piezoceramic system. (C) 2014 Elsevier Ltd. All rights reserved.Postprint (published version

Densification par Spark Plasma Sintering (SPS) de matériaux d’électrolytes, difficilement densifiables, pour piles à combustible

Des matériaux tels que les apatites à base d’oxydes de lanthane et de silicium ou des pérovskites conductrices protoniques, potentiellement utilisables au sein de piles à combustible, présentent une grande résistance au frittage. Celle-ci limite d’autant plus leur utilisation au sein de piles à combustible, surtout s’ils doivent être employés comme électrolytes. Plusieurs stratégies peuvent être envisagées pour remédier à ce problème parmi lesquelles l’emploi de nouvelles méthodes de frittage ou le choix d’une méthode de synthèse efficace (permettant par exemple de diminuer la taille des grains ou de limiter celle des agrégats souvent rédhibitoires au moment du frittage). Nous présentons ici les résultats de frittage par Spark Plasma Sintering (appelé par la suite SPS) en les comparants à ceux obtenus par frittage conventionnel haute température. Les matériaux étudiés ont des compositions dérivées des phases La9,330,67Si6O26 et BaZr0,9Y0,1O2,950,05 pour lesquelles des problèmes de frittage ont été rencontrés. Nous insisterons sur les particularités des matériaux obtenus par SPS en termes de structure et microstructure et des conséquences sur les propriétés de transport anionique

Influence of synthesis route and composition on electrical properties of La9.33 + xSi6O26 + 3x/2 oxy-apatite compounds

Oxy-apatite materials La9.33 + xSi6O26 + 3x/2 are thought as zirconia-substitutes in Solid Oxide Fuel Cells due to their fast ionic conduction. However, the well-known difficulties related to their densification prevent them from being used as such. This paper presents strategies to obtain oxyapatite dense materials. First, freeze-drying has been optimized to obtain ultrafine and very homogeneous La9.33 + xSi6O26 + 3x/2 (0≤x≤0.67) nanopowders. From these powders, conventional and Spark Plasma Sintering (SPS) have been used leading to very dense samples obtained at temperatures rather lower than those previously reported. For instance, SPS has allowed to prepare fully dense and transparent ceramics from 1200 °C under 100 MPa. The microstructure and transport properties of such samples have been then evaluated as a function of sintering conditions and lanthanum content. It will be show that for lanthanum content higher than 9.60 per unit formula, the parasitic phase La2SiO5 appears leading to a egradation of conduction properties.We also show that grain boundaries and porosity (for conventionally-sintered materials) seem to have blocking effects on oxygen transport. The highest overall conductivity values at 700 °C, i.e. σ700 °C=7.33.10−3 S cm−1, were measured for La9.33Si6O26 material conventionally-sintered at 1500 °C which contains bigger grains' size by comparison with σ700 °C=4.77.10−3 S cm−1 for SPS-sintered materials at the same temperature but for few minutes. These values are associated with activation energies close to 0.83–0.91 eV, regardless of sintering condition, which are commonly encountered for anionic conductivity into such materials

Improving the functional properties of (K0.5Na0.5)NbO3 piezoceramics by acceptor doping

ZrO2 and TiO2 modified lead-free (K0.5Na0.5)NbO3 (KNN) piezoelectric ceramics are prepared by conventional solid-state reaction. The effect of acceptor doping on structural and functional properties are investigated. A decrease in the Curie temperature and an increase in the dielectric constant values are observed when doping. More interestingly, an increase in the coercive field Ec and remanent polarization Pr is observed. The piezoelectric properties are greatly increased when doping with small concentrations dopants. ZrO2 doped ceramic exhibits good piezoelectric properties with piezoelectric coefficient d33=134 pC/N and electromechanical coupling factor kp=35%. It is verified that nonlinearity is significantly reduced. Thus, the creation of complex defects capable of pinning the domain wall motion is enhanced with doping, probably due to by the formation of oxygen vacancies. These results strongly suggest that compositional engineering using low concentrations of acceptor doping is a good means of improving the functional properties of KNN lead-free piezoceramic system

Effects of Cation Vacancy Distribution in Doped LaMnO3+d Perovskites

In this paper we report studies on the correlation between the presence and distribution of cation vacancies in doped manganites (La,M)MnO3+delta (where M = Na, Ca) and their magnetic properties. Results indicate that cation vacancies are distributed differently for the different crystal structures and dopant ion type. In particular it is shown that knowledge of the total vacancies concentration alone is not enough to fully characterize the physical properties of manganites and that their distribution between the A and B sites of the perovskite structure plays a crucial role which should be taken into account in future studies.Comment: 27 pages, 5 figure. To appear in J. Solid State Che

Preparation of transparent oxyapatite ceramics by combined use of freeze-drying and spark-plasma sintering

Lanthanum silicate oxyapatites, ion-conducting materials presenting a strong aversion against densification, have been obtained in the form of dense transparent ceramics, by combining the beneficial use of freeze-drying and spark plasma sintering methods