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

A comprehensive thermodynamic study of the U-Am-O ternary system: multiple experimental investigations and Calphad modelling

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Investigation of the solid/liquid phase transitions in the U–Pu–O system

Mixed oxides of uranium and plutonium U1-yPuyO2-x are currently studied as reference fuel for Sodium-cooled Fast Reactors (SFRs). To predict the margin to fuel melting, an accurate description of both solidus and liquidus temperatures of these materials is crucial. In this work, after a critical review of the literature data, the parameters of the liquid phase of the CALPHAD models of the Pu–O and U–Pu–O systems are reassessed based on the model of Gu´eneau et al.. A good agreement between the calculated and selected experimental data is obtained. Using this model, the melting behaviour of U1-yPuyO2±x oxides is then studied as a function of plutonium content and oxygen stoichiometry. The congruent melting for the mixed oxides is found to be shifted towards low O/M ratios compared to the end-members (UO1.97 and PuO1.95). The temperature of this congruent melting is nearly constant (3130–3140 K) along a ternary phase boundary from UO1.98 to U0.55Pu0.45O1.82 and then decreases with Pu content to a maximum of approximately 3040 K for PuO1.95. This observation is explained by the stabilisation of the hypo-stoichiometric mixed oxides due to the increase of the configurational entropy at high temperatures by the formation of oxygen vacancies and related cation mixing. The influence of the atmosphere used in the laser heating melting experiments on the oxygen stoichiometry of the sample and its solidus and liquidus temperatures is investigated. The determination of this O/M ratio after laser melting tests using XANES is also reported. The simultaneous presence of U6+, U5+, U4+, Pu3+ and Pu4+ is observed, highlighting the occurrence of charge compensation mechanisms. The samples are highly oxidised in air whereas close to stoichiometry (O/M = 2.00) in argon. These results are in agreement with the computed solidification paths. This work illustrates the complex melting behaviour of the U1-yPuyO2±x fuels and highlights the need for the CALPHAD method to accurately describe and predict the high-temperature transitions of the U–Pu–O system

Melting behaviour of uranium-americium mixed oxides under different atmospheres

In the context of a comprehensive campaign for the characterisation of transmutation fuels for next generation nuclear reactors, the melting behaviour of mixed uranium-americium dioxides has been experimentally studied for the first time by laser heating, for Am concentrations up to 70 mol. % under different types of atmospheres. Extensive post-melting material characterisations were then performed by X-ray absorption spectroscopy and electron microscopy. The melting temperatures observed for the various compositions follow a markedly different trend depending on the experimental atmosphere. Uranium-rich samples melt at temperatures significantly lower (around 2700 K) when they are laser-heated in a strongly oxidizing atmosphere compressed air at (0.300 ± 0.005) MPa, compared to the melting points (beyond 3000 K) registered for the same compositions in an inert environment (pressurised Ar). This behaviour has been interpreted on the basis of the strong oxidation of such samples in air, leading to lower-melting temperatures. Thus, the melting temperature trend observed in air is characterized, in the purely pseudo-binary dioxide plane, by an apparent maximum melting temperature around 2850 K for 0.3 < x(AmO2) < 0.5. The melting points measured under inert atmosphere uniformly decrease with increasing americium content, displaying an approximately ideal solution behaviour if a melting point around 2386 K is assumed for pure AmO2. In reality, it will be shown that the (U, Am)-oxide system can only be rigorously described in the ternary U-Am-O phase diagram, rather than the UO2-AmO2 pseudo-binary, due to the aforementioned over-oxidation effect in air. Indeed, general departures from the oxygen stoichiometry (Oxygen/Metal ratios ≠ 2.0) have been highlighted by the X-ray Absorption Spectroscopy (XAS). Finally, to help interpret the experimental results, thermodynamic computations based on the CALPHAD method will be presented

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

Thermodynamic assessment of the palladium-tellurium (Pd-Te) system

International audienceAmong the fission products formed in nuclear fuels, the platinum-group metal palladium and the chalcogen element tellurium exhibit strong interaction. It is therefore of interest to be able to predict the chemical equilibria involving the Pd and Te fission products. A thermodynamic assessment is carried out using the Calphad (Calculation of Phase Diagram) method to investigate the behaviour of Pd-Te alloy system in nuclear fuels under irradiation and under waste disposal conditions. The Pd-Te binary description was optimized using experimental data found in literature including thermodynamic properties and phase diagram data. To validate the calculated phase diagram and thermodynamic properties, the results are compared with data from the literature. Both calculated and experimental phase diagrams and thermodynamic properties are in good agreement in the whole Pd-Te composition range

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+}