Virgil Optasanu

A thermodynamic approach of the mechano-chemical coupling during the oxidation of uranium dioxide

The aim of the present work is to introduce a thermodynamic model to describe the growth of an oxide layer on a metallic substrate. More precisely, this paper offers a study of oxygen dissolution into a solid, and its consequences on the apparition of mechanical stresses. They strongly influence the oxidation processes and may be, in some materials, responsible for cracking. To realize this study, mechanical considerations are introduced into the classical diffusion laws. Simulations were made for the particular case of uranium dioxide, which undergoes the chemical fragmentation. According to our simulations, the hypothesis of a compression stress field into the oxidised UO2 compound near the internal interface is consistent with the interpretation of the mechanisms of oxidation observed experimentally.

Simulation of Metal/Oxide Interface Mobility: Effects of Mechanical Stresses on Geometrical Singularities

During the last decade, an increasing importance has been given to the feedback of mechanical stresses on the chemical diffusion and, further, on corrosion. Many works point the active role of stresses on the material ageing especially on their negative consequences leading to the damaging of structures. Based on a theoretical study and using numerical tools and experimental results our previous works [1, on stress/diffusion coupling, highlight the strong influence of stress field on the diffusion process. The aim of the present paper is to describe the influence of some particular morphologies of the metal/oxide interface on both diffusion and oxidation process. The oxidation is assumed to be driven by a mass conservation law (Stefans law) while the diffusion coefficient of oxygen in metal is locally influenced by the stress field. The stability of a waved-shape interface is studied in both cases: simple diffusion and coupled stress/diffusion process. In this purpose we have developed an original numerical model using a virtual metal/oxide interface of a mono-material with oxygen concentration-dependent parameters, which allows to operate easily with any shape of interface and to use simple finite element meshes. Furthermore, in order to underline in a more obvious way the consequences of mechanical stress on the diffusion process, a particular geometry is studied.

Pre-Stressed Sub-Surface Contribution on Bulk Diffusion in Metallic Solids

Our recent modelling works and corresponding numerical simulations realized to describe the UO2 oxidation processes confirm the theory showing that an applied mechanical strain can strongly affect the local oxygen diffusion in a stressed solid. This result allows us to assume that stress field, previously applied at the surface of a metallic sample on several microns, will delay the degradation during its oxidation. Considering this hypothesis, we implemented a FEM simulation code developed in our laboratory to numerically investigate some different stress fields applied on a sample sub-surface, that might significantly modify the volume diffusion of oxygen during the oxidation process. The results of our simulations are presented and discussed from the perspective to study the consequences of a surface mechanical treatment on the durability of a metallic material.

Internal Interface Strains Effects on UO2/U3O7 Oxidation Behaviour

The growth of a U3O7 oxide layer during the anionic oxidation of UO2 pellets induced very important mechanical stresses due to the crystallographic lattice parameters differences between UO2 and its oxide. These stresses, combined with the chemical processes of oxidation, can lead to the cracking of the system, called chemical fragmentation. We study the crystallographic orientation of the oxide lattice growing at the surface of UO2, pointing to the fact that epitaxy relations at interface govern the coexistence of UO2 and U3O7. In this work, several results are given: - Determination of the epitaxy relations between the substrate and its oxide thanks to the Bollmann’s method; epitaxy strains are deduced. - Study of the coexistence of different domains in the U3O7 (crystallographic compatibility conditions at the interface between two phases: Hadamard conditions). - FEM simulations of a multi-domain U3O7 connected to a UO2 substrate explain the existence of a critical thickness of U3O7 layer.

Specific Aspects of Internal Corrosion of Nuclear Clad Made of Zircaloy

In PWR, the Zircaloy based clad is the first safety barrier of the fuel rod, it must prevent the dispersion of the radioactive elements, which are formed by fission inside the UO2 pellets filling the clad. We focus here on internal corrosion that occurs when the clad is in tight contact with the UO2 pellet. In this situation, with temperature of 400 °C on the internal surface of the clad, a layer of oxidised Zircaloy is formed with a thickness ranging from 5 to 15 µm. In this paper, we will underline the specific behaviour of this internal corrosion layer compared to wet corrosion of Zircaloy. Simulations will underline the differences of stress field and their influences on corresponding dissolved oxygen profiles. The reasons for these differences will be discussed as function of the mechanical state at inner surface of the clad which is highly compressed. Differences between mechanical conditions generated by an inner or outer corrosion of the clad are studied and their influences on the diffusion phenomena are highlighted.

Characterization of Oxygen-Enriched Layers of TA6V, Titanium, and Zirconium by Scanning Microwave Microscopy

A technique based on scanning microwave microscopy (SMM) has recently been developed to analyze solid solutions of light elements. This technique consists in local measurements of effects produced by electrical conductivity variations produced by light elements solutions in metals. The penetration of the microwaves into the metals depends on their frequency and the material parameters. Information regarding the local conductivity of the material at different depths can be recorded using various frequencies. In this paper, SMM measurements of the oxygen-enriched zone are presented for several materials: TA6V, pure Ti, and pure Zr. Comparisons with concentration measurements made by nuclear reaction analysis allow one to affirm that for all the materials investigated here the phase shift measured by SMM is proportional to the oxygen concentration dissolved into the metal. Calibration functions are proposed for each material and frequency used. After calibration, the SMM can be used to measure local enrichments.

Calcite and barite precipitation in CaCO3-BaSO4-NaCl and BaSO4-NaCl-CaCl2 aqueous systems: kinetic and microstructural study

During the production of hydrocarbons from subterranean reservoirs, scaling with calcium carbonate and barium sulfate causes flux decline and dangerous problems in production facilities. This work is intended to study the effect of calcium ions on the precipitation of barium sulfate (barite); then, the effect of the formed barite on calcium carbonate crystallization. The conductometric and pH methods were used to follow the progress of the precipitation reaction in aqueous medium. The obtained precipitates were characterized by FTIR, RAMAN, SEM, and XRD. It was shown that Ca2+ in the reaction media does not affect the microstructure of barite even for higher calcium–barium molar ratio. It influences the precipitation kinetics and the solubility of barite by the formation of CaSO4° ion pairing as a predominant role of complex formation (CaSO4) and the increase of the ionic strength. In Ca(HCO3)2-BaSO4-NaCl aqueous system, experiments have showed that added or formed barite in the reaction media accelerates calcite precipitation. No effect on the microstructure of heterogeneous formed calcite which remain calcite shape. However the presence of carbonate ions affects slightly the microstructure of barite.

SOLID SOLUTION CHARACTERIZATION IN METAL BY ORIGINAL TOMOGRAPHIC SCANNING MICROWAVE MICROSCOPY TECHNIQUE

A general challenge in metallic components is the need for materials research to improve the service lifetime of the structural tanks or tubes subjected to harsh environments or the storage medium for the products. One major problem is the formation of lightest chemical elements bubbles or different chemical association, which can have a significant impact on the mechanical properties and structural stability of materials. The high migration mobility of these light chemical elements in solids presents a challenge for experimental characterization. Here, we present work relating to an original non-destructive, with high spatial resolution, tomographic technique based on Scanning Microwave Microscopy (SMM), which is used to visualize in-depth chemical composition of solid solution of a light chemical element in a metal. The experiments showed the capacity of SMM to detect volume. Measurements realized at different frequencies give access to a tomographic study of the sample.

A Mechano-Chemical Coupling for Hydrogen Diffusion in Metals Based on a Thermodynamic Approach

Hydrogen diffusion in metals is still an ongoing topic of research due to its technical relevance (hydrogen embrittlement, hydrogen storage...). In the last decades, significant progress in understanding the time evolution of the hydrogen concentration in solids was completed. This paper presents a modeling of hydrogen diffusion with a general and thermodynamically based diffusion concept coupled with mechanical and chemical aspects. This model was previously used to simulate the oxidation of a metal [1][2]. This concept has been upgraded to offer a thoroughly macroscopic behavior law used to simulate hydrogen diffusion in metal parts under mechanical loadings. The thermodynamic approach of the stress-diffusion coupling was implemented in a finite element code in order to study the hydrogen diffusion mode into a strained metal. Simulations were performed on a cylindrical austenitic steel tank under important internal pressure. The results of this study allow us to understand how hydrogen diffusion and mechanical stresses are mutually induced and modified.