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Evangelakis, Georges
Universite Nancy I (France); Centre d'Etudes Nucleaires de Saclay - CEA, Institut de Recherche Technologique et de Developpement Industriel, Division de Metallurgie et d'Etude des Combustibles Nucleaires, Departement de Technologie (France); Universite de Ioannina, Laboratoire de Physique Appliquee (Greece)1989
Universite Nancy I (France); Centre d'Etudes Nucleaires de Saclay - CEA, Institut de Recherche Technologique et de Developpement Industriel, Division de Metallurgie et d'Etude des Combustibles Nucleaires, Departement de Technologie (France); Universite de Ioannina, Laboratoire de Physique Appliquee (Greece)1989
AbstractAbstract
[en] In this work we present the results of an experimental study concerning the superionic conductivity of SrF2 and those obtained by an investigation of the thermodynamical properties of CaF2 using molecular dynamics simulation in the superionic region. The conductivity measurements in SrF2 have been performed at high temperatures (700-1350 K) and various frequencies (10 Hz-10 MHz). At each temperature a frequency dependence of the conductivity has been detected. The analysis of the results using complex impedance diagrams revealed that this dependence is not an intrinsic property of the material but is related to electrodes effects. The apparent activation energies associated to the different parts of the intrinsic and extrinsic conductivity regions have been determined. Unfortunately no clear conclusion relative to the conduction mechanism can be made there from. Computer simulations by molecular dynamics have been performed in CaF2 modeled using a rigid ion potential. The diffusion coefficient, the specific heat, structure factors, mean square displacements of both anions and cations, as well as the temperature dependence of these quantities have been calculated. The good agreement found between calculated quantities and experimental results justified us in using the crude approximation of a rigid on potential. A direct computation of the superionic conductivity has been obtained for the first time using non-equilibrium molecular dynamics in the linear response regime. From the independent calculation of the diffusion coefficient and the conductivity, the Havens ratio has been deduced, Hr 0.34, in the superionic region. Its value suggests that the superionic conductivity of CaF2 is due to a collective and correlated mechanism, a fact which has been confirmed by the MD trajectory analysis. (author)
[fr]
Dans ce travail nous presentons les resultats d'une etude experimentale de la conductivite ionique du SrF2, ainsi que ceux d'une investigation des proprietes thermodynamiques du CaF2 dans le domaine de conduction superionique par simulation a l'aide de la Dynamique Moleculaire. Les mesures de la conductivite ionique du SrF2 ont ete effectuees a haute temperature (700-1350 K) en fonction de la frequence du champ electrique utilise (10 Hz-10 MHz). Pour toutes les temperatures exploitees, nous avons trouve une dependance de la conductivite en fonction de la frequence. L'analyse des resultats au moyen de diagrammes d'impedance complexe a montre que cette dependance est due aux mauvais contacts entre l'echantillon et les electrodes. L'utilisation de ces diagrammes a permis de determiner la conductivite intrinseque du materiau. Des diagrammes d'Arrhenius pour la conductivite nous avons pu determiner les energies d'activation apparentes pour les differentes regions de conduction. Celles-ci ne permettent malheureusement pas d'identifier les mecanismes atomiques de superconductivite ionique. La simulation par la Dynamique Moleculaire (DM) du CaF2 a ete effectuee en utilisant un potentiel d'ions rigides. Nous avons calcule la constante de diffusion, le facteur de structure, la chaleur specifique, le deplacement quadratique moyen et leur variation en fonction de la temperature. Les resultats sont en bon accord avec l'experience, ce qui justifie a posteriori le choix du potentiel. En utilisant la DM hors d'equilibre dans la region de reponse lineaire, la superconductivite ionique du CaF2 a pu etre obtenue. Les calculs independants de la conductivite et de la constante de diffusion, fournissent le rapport de Haven Hr 0.34, dans la region superionique. Cette valeur suggere que la superconductivite ionique de ce materiau est due a un mecanisme collectif et correle ce qui est confirme par l'analyse des trajectoires des particules. (auteur)Original Title
Superconducteurs ioniques de structure fluorine: a) Mesure de la conductivite ionique du SrF2 a haute temperature, b) Etude des proprietes thermodynamiques du CaF2 par simulation numerique
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28 Sep 1989; 156 p; 165 refs.; Available from the INIS Liaison Officer for France, see the 'INIS contacts' section of the INIS website for current contact and E-mail addresses: http://www.iaea.org/inis/contacts/; These Docteur de l'Universite de Nancy I, Specialite: Physique
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Report
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Thesis/Dissertation
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CALCIUM FLUORIDES, COMPUTERIZED SIMULATION, DIFFUSION, ELECTRIC BATTERIES, FREQUENCY DEPENDENCE, FUEL CELLS, IMPEDANCE, IONIC CONDUCTIVITY, MOLECULAR DYNAMICS METHOD, SOLID ELECTROLYTES, STRONTIUM FLUORIDES, SUPERCONDUCTIVITY, TEMPERATURE RANGE 0400-1000 K, TEMPERATURE RANGE 1000-4000 K, THERMODYNAMIC PROPERTIES
ALKALINE EARTH METAL COMPOUNDS, CALCIUM COMPOUNDS, CALCIUM HALIDES, CALCULATION METHODS, DIRECT ENERGY CONVERTERS, ELECTRIC CONDUCTIVITY, ELECTRICAL PROPERTIES, ELECTROCHEMICAL CELLS, ELECTROLYTES, ENERGY STORAGE SYSTEMS, ENERGY SYSTEMS, FLUORIDES, FLUORINE COMPOUNDS, HALIDES, HALOGEN COMPOUNDS, PHYSICAL PROPERTIES, SIMULATION, STRONTIUM COMPOUNDS, STRONTIUM HALIDES, TEMPERATURE RANGE
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