Marc Tupin

Imaging by photoelectrochemical techniques of Laves-phases γ-Zr(Fe,Cr)2 thermally oxidized on Zircaloy-4

The oxidation of γ-Zr(Fe,Cr)2 intermetallic particles during the thermal exposition of Zircaloy-4 at 470°C in oxygen was investigated with PhotoElectroChemical techniques (PEC). Via the measurement of bandgap, haematite Fe2O3 (2.2 eV), rhomboedric solid solution (FexCr1-x)2O3 (2.6 eV) and chromia Cr2O3 (3.0 eV) phases were identified as components of oxidised particles. Evolution of size, lateral distribution and density of these particles was studied in function of zirconia scale thickness. During the first stage of oxidation, the density of oxidised particles increased with thickness but decreased during a second stage, highlighting in an innovative way the phenomenon of haematite and chromia dissolution in the zirconia matrix. It is concluded that PEC techniques represent a sensitive and powerful way to locally analyse the various semiconductor phases in an oxide scale at the micron scale.

Microstructure and Properties of a Three-Layer Nuclear Fuel Cladding Prototype Containing Erbium as a Neutronic Burnable Poison

To increase cycle length and/or fuel burnup, several theoretical and experimental studies have been performed at CEA. Among them, prospective neutronic calculations have shown that the addition of a few weight percents of erbium into the cladding materials could be a promising alternative to the introduction of the neutronic poison directly into the nuclear fuel pellets. Thus, fabrication of homogeneous Zr-Er alloys has been assessed, at least up to 10 wt. % of erbium and, based on the as-received mechanical properties, an optimum erbium concentration ranging from 3 to 6 wt. % has been derived. However, because of the high-oxygen thermodynamic affinity of erbium, thermal treatments have to be controlled during the fabrication route to limit Er2O3 precipitation and coarsening, which may have detrimental effects on the ductility/toughness of Zr-Er alloys. In parallel, to get more fundamental insights into the underlying phase diagrams, thermodynamic studies have been devoted to experimental assessment and modeling of the Zr-Er-(H-O) system. Because of the detrimental influence of erbium on the corrosion resistance, a three-layer sandwich clad prototype has been developed using corrosion-resistant inner/outer Zr-1Nb layers to protect the intermediate Zr-Er layer from direct water exposure. Compared to a reference Zr-1Nb(O) alloy that has been subjected to the same fabrication route, the three-layer clad prototype shows limited decrease in ductility because of pre-hydriding or after high-temperature steam oxidation e.g., in the case of a loss-of-coolant accident). Moreover, the studies performed so far have shown a spectacular hydride trapping capacity of the intermediate Zr-Er layer both for hydrogen coming from nominal outer corrosion or because of massive secondary hydriding in case of the direct access of water to the Zr-Er intermediate layer. Using μ-ERDA (elastic recoil detection analysis) measurements, detailed studies of the hydrogen spatial redistribution upon thermal cycling has been done. A simple model has been successfully used to characterize the cooling rate influence on the through-wall clad thickness partitioning of hydrogen/hydrides between the three layers, after cooling from a temperature corresponding to full dissolution of hydrides

Corrosion of M5 in PWRs: Quantification of Li, B, H and Nb in the Oxide Layers Formed Under Different Conditions

Until now, most of the detailed characterizations of the M5 corrosion behaviour were performed under standard PWR operating conditions, under moderate Li content and moderate temperature of the primary coolant. In this study, in addition to these standard conditions, two demanding operating conditions were explored: increased Li chemistry and elevated temperature. The objective is to establish whether these more demanding conditions have an impact on the structure of the oxide layers formed, on Nb, Li and B contents in these layers and on Hydrogen pickup of the cladding. The structure of oxide layers was studied by microscopy, the Nb content and distribution by Electron Probe Micro Analysis, the Li and B contents and distributions by Nuclear Reaction Analysis and the hydrogen pickup by gas extraction. It was observed that the stability of the corrosion behaviour of M5 is not affected by increased Li or elevated temperature conditions. The hydrogen pickup fraction of M5 is not modified by increased Li conditions or by irradiation temperature with measured contents (

Understanding of Corrosion Mechanisms after Irradiation: Effect of Ion Irradiation of the Oxide Layers on the Corrosion Rate of M5

Irradiation damage in fuel cladding material is mainly caused by the neutron flux that results from fission reactions occurring in the fuel. To avoid the constraints inherent in handling radioactive material, the irradiation effects on the corrosion resistance of zirconium alloys can be studied by irradiating the materials with ions. We performed an original experiment using ion irradiation to more specifically study the influence of irradiation damage in the oxide on the corrosion rate of M5®. It has been established that irradiation with a 1.3-MeV helium ion at a fluence of 1017 cm−2 results in significant modifications of oxide properties, oxygen diffusion flux, and oxidation kinetics, as evidenced by Raman spectroscopy, secondary ion mass spectrometry (SIMS) analyses, and measurements of mass gains. A newly identified Raman vibration band at 712 cm−1 was linked to the presence of irradiation defects and allowed the evolution of their concentrations to be followed. The oxygen diffusion flux was significantly reduced after irradiation partly due to a surface concentration decrease of oxygen. The defects remained present in the oxide after 100 days of annealing in pressurized water reactor (PWR) conditions and were thus very stable in PWR conditions, which probably means that these defects would be stable in the reactor. According to the kinetics and in agreement with the results obtained by SIMS analyses, the oxidation rate was significantly reduced after ion irradiation, and this effect remained beyond 100 days in agreement with the high stability of irradiation defects in PWR conditions. An original model described quite well the oxidation kinetic results.