Lopez, Christophe
CEA Marcoule, Dept. d'Ingenierie et d'Etudes des Confinements, 30 (France)2003
CEA Marcoule, Dept. d'Ingenierie et d'Etudes des Confinements, 30 (France)2003
AbstractAbstract
[en] The nuclear wastes are currently incorporated in borosilicate glass matrices. The resulting glass must be perfectly homogeneous. The work discussed here is a study of actinide (thorium and plutonium) solubility in borosilicate glass, undertaken to assess the extent of actinide solubility in the glass and to understand the mechanisms controlling actinide solubilization. Glass specimens containing; actinide surrogates were used to prepare and optimize the fabrication of radioactive glass samples. These preliminary studies revealed that actinide Surrogates solubility in the glass was enhanced by controlling the processing temperature, the dissolution kinetic of the surrogate precursors, the glass composition and the oxidizing versus reducing conditions. The actinide solubility was investigated in the borosilicate glass. The evolution of thorium solubility in borosilicate glass was determined for temperatures ranging from 1200 deg C to 1400 deg C.Borosilicate glass specimens containing plutonium were fabricated. The experimental result showed that the plutonium solubility limit ranged from 1 to 2.5 wt% PuO2 at 1200 deg C. A structural approach based on the determination of the local structure around actinides and their surrogates by EXAFS spectroscopy was used to determine their structural role in the glass and the nature of their bonding with the vitreous network. This approach revealed a correlation between the length of these bonds and the solubility of the actinides and their surrogates. (author)
[fr]
Les verres utilises pour le confinement des dechets niucleaires doivent etre completement homogenes. Il est donc capital d'identifier les limites d'incorporation dans les verres des differents elements constituant ces dechets et d'identifier les mecanismes qui ]pilotent leur solubilisation. C'est dans ce cadre que s'inscrit ce travail dont l'objectif est l'etude de la solubilite des actinides (thorium et plutonium) dans les verres borosilicates nucleaires. Du fait de la complexite des experiences menees en milieu radioactif, une etude preliminaire a ete entreprise en utilisant des elements non radioactifs simulant le comportement des actinides dans les verres. Cette etude a permis de mettre en evidence les principaux parametres d'elaboration susceptibles d'augmenter les limites de solubilite de ces elements. Il s'agit de la temperature d'elaboration des verres, des parametres ayant une influence sur la cinetique de dissolution des precurseurs des simulants des actinides dans le bain fondu, de la composition du verre et des conditions oxydoreductrices regnant lors de l'elaboration. De:s verres borosilicates contenant des actinides ont ensuite ete etudies. L'evolution de la limite de solubilite du thorium dans un verre borosilicate en fonction de la temperature a ete determinee entre 1200°C et 1400°C. Les experiences d'elaboration de verres borosilicates contenant du plutonium ont montre que la limite de solubilite de cet element dans ces verres est comprise entre 1 et 2,5 % massiques de PuO2 a 1200°C. Une approche structurale basee sur les resultats de la caracterisation de la structure locale autour des actinides et des simulants par spectroscopie EXAFS a permis d'emettre des hypotheses quant au role structural de ces elements et a la nature des liaisons qu'ils engagent dans le reseau vitreux. Cette approche a egalement mis en evidence une correlation directe entre la longueur de ces liaisons et la solubilite de ces elements. (auteur)Original Title
Solubilite des actinides et de leurs simulants dans les verres nucleaires. Limites d'incorporation et comprehension des mecanismes
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Feb 2003; 244 p; Available from the INIS Liaison Officer for France, see the INIS website for current contact and E-mail addresses; This record replaces 35009608; These (Docteur en Science)
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AbstractAbstract
[en] The evolution of the sites occupied by cerium and neodymium (coordination numbers and Ce, Nd-O distances) during alteration of simplified SON68 glass specimens was determined by LIII-edge XAS. Cerium and neodymium are situated in a silicate environment in the glass, surrounded by eight oxygen atoms at an average distance of 2.44 and 2.48 A, respectively. These two rare earth elements exhibit different leaching behavior, however. The main environment of cerium becomes a silicate (d Ce-O = 2.19 A) with a second oxide or more probably oxyhydroxide site (d Ce-O = 2.32 A). The cerium coordination number increases by 1 to 3 compared with the glass, depending on the leaching conditions. Neodymium is found mainly in a hydroxycarbonate environment (d Nd-O = 2.46 A); the second site is a silicate (d Nd-O = 2.54 A). The neodymium coordination number increases by 1 compared with the glass. When glass containing neodymium is doped with phosphorus, Nd is situated in a phosphate environment; this change is also reflected in the coordination number and Nd-O distance (seven oxygen atoms at 2.42 A). During glass leaching, neodymium is present at two different sites, phosphate (d Nd-O = 2.52 A) and hydroxycarbonate (d Nd-O = 2.40 A)
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S0022-3115(05)00306-5; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
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