A Thermodynamic Approach to Predict the Metallic and Oxide Phases Precipitations in Nuclear Waste Glass Melts

AbstractAmong the large number of matrixes explored as hosts for high-level nuclear wastes, conditioning of fission products and minor actinides into a homogeneous borosilicate glass is the most promising technique already implemented at the industrial scale. The advantage of this vitrification process is the volume reduction of the high level waste coming from the spent fuel reprocessing and its stability for the long-term storage. Nevertheless, some fission products are poorly soluble in molten glasses:•Platinoids (Pd, Ru, Rh) which precipitate as (Pd-Te, Ru-Rh) metallic particles and (Rh,Ru)O2 oxide phases with acicular or polyhedral shapes during the vitrification process.•Molybdenum oxide (MoO3) which can form complex molybdates.In order to point out the chemical interactions between the glass and these precipitated phases issuing from the calcinated waste, a thermodynamic approach is developed using the Calphad method. The objective of this work is to calculate thermodynamic properties for complex fission product systems in order to predict the precipitation of platinoids or molybdate phases.This thermodynamic database is being developed on the Mo-Pd-Rh-Ru-Se-Te-O complex system. This flexible tool enables to predict phase diagrams, composition and relative stability of the metallic or oxide precipitated phases as a function of both temperature and oxygen potential in the glass melt

Extreme multi-valence states in mixed actinide oxides

To assure the safety of oxide-fuel based nuclear reactors, the knowledge of the atomic-scale properties of U1−yMyO2±x materials is essential. These compounds show complex chemical properties, originating from the fact that actinides and rare earths may occur with different oxidation states. In these mostly ionic materials, aliovalent cationic configurations can induce changes in the oxygen stoichiometry, with dramatic effects on the properties of the fuel. First studies on U1−yAmyO2±x indicated that these materials exhibit particularly complex electronic and local-structure configurations. Here we present an in-depth study of these compounds, over a wide compositional domain, by combining XRD, XAS and Raman spectroscopy. We provide evidences of the co-existence of four different cations (U4+, U5+, Am3+, Am4+) in U1−yMyO2±x compounds, which nevertheless maintain the fluorite structure. Indeed, we show that the cationic sublattice is basically unaffected by the extreme multi-valence states, whereas complex defects are present in the oxygen sublattice

Program Verification in the Presence of I/O

Software veri?cation tools that build machine-checked proofs of functional correctness usually focus on the algorithmic content of the code. Their proofs are not grounded in a formal semantic model of the environment that the program runs in, or the program’s interaction with that environment. As a result, several layers of translation and wrapper code must be trusted. In contrast, the CakeML project focuses on endto-end veri?cation to replace this trusted code with veri?ed code in a cost-e?ective manner. In this paper, we present infrastructure for developing and verifying impure functional programs with I/O and imperative ?le handling. Specifically, we extend CakeML with a low-level model of ?le I/O, and verify a high-level ?le I/O library in terms of the model. We use this library to develop and verify several Unix-style command-line utilities: cat, sort, grep, di? and patch. The work?ow we present is built around the HOL4 theorem prover, and therefore all our results have machine-checked proofs

Modelling of plutonium diffusion in (U,Pu)O2±x_{2±x} mixed oxide

International audienceThe modelling of the thermo-kinetic properties of uranium-plutonium mixed oxide (MOX) is of utmost importance for optimizing its synthesis and for predicting its behaviour in Fast Breeder Reactors. Despite the 10 stakes and likely because of experimental issues, little or no experimental data are available for the entire MOX system. We circumvent here the difficulties by developing a mobility database for plutonium using the DICTRA code. A well-established model of MOX formalized within the Compound Energy Formalism ensures the thermodynamic description. Rationalisation of the mobility parameters combined with the use of both cBΩ model and the few experimental data lead to a full and comprehensive description of plutonium self-diffusion in 15 MOX for any plutonium content, O/M ratio and temperature. Additionally, we show that the observed plateau of the self-diffusion as a function of the oxygen to metal ratio (O/M) is related to the constant Pu$^{3+}$ fraction for very low O/M ratio. Moreover, the observed minimum close to O/M = 2 is found for the lowest mobility of Pu$^{4+}

High temperature corrosion phenomena during a nuclear severe accident - The corium-concrete interaction

International audienceDuring a severe accident in a nuclear reactor, extreme temperatures may be reached (T>2500 K). In these conditions, the nuclear fuel may react with the Zircaloy cladding and then with the steel vessel, forming a mixture of solid-liquid phases called in-vessel corium. In the worst scenario, this mixture may pierce the vessel and reach the concrete underneath the reactor. Many phenomena take place during MCCI (Molten Core Concrete Interaction) high temperature concrete ablation/decomposition, heat transfer due to gas bubbles agitation, formation of several phases, oxidation of metals, etc. Several studies on the interaction between corium and concrete were published starting from the 1980s; in particular numerous large scale experiments were performed on this subject. Although large scale experiments answer to macro-scale phenomena, such as ablation profile, corium flooding behaviour, coolability of the molten core, density and viscosity evolution, etc., the interpretation of the microstructure of the post-experiments sample is rather challenging. In this framework a campaign of small-scale experiments is ongoing on prototypic corium+concrete system U-Zr-Ca-Si-Al-O. These tests provide useful data for the comprehension of the phenomena occurring during a severe accident, when the molten corium reaches the concrete underneath the damaged steel vessel. It has been observed that depending on the composition of the concrete (more of less rich in SiO$_2$), the final configuration of the ex-vessel corium (i.e., after the in-vessel corium/concrete interaction) can be significantly differen

Les normes dans la régulation mondiale des marchés et des acitvités économiques

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Experimental and calculation investigation on severe accidents in PWR reactors

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