Laure Martinelli

A precise methodology for determining the growth mode of oxide layers on metallic materials at high temperatures is proposed. The approach combines sequential isotopic oxidation tests (using ¹⁶ O and ¹⁸ O isotopes) with secondary ion mass spectrometry (SIMS and nanoSIMS) analyses. NanoSIMS provides high-resolution localisation of oxygen diffusion pathways and oxide growth zones. However, its limited accessibility and specialised instrumentation can pose practical constraints. In contrast, dynamic SIMS offers broader accessibility and the ability to directly quantify oxygen isotope ratios across depth profiles. The detection of both conventional atomic (O ⁻ ) and diatomic (O ₂ ⁻ ) oxygen signals in dynamic SIMS analysis proved highly effective in offering insights on oxide growth mode, closely replicating nanoSIMS results. The diatomic signal analysis complements the atomic signal data by improving the understanding of oxidant transport within the oxide layer. The methodology was validated through its application to a Co-10Cr alloy oxidised at 900 °C in O ₂ , under sequential exposures to ¹⁶ O and ¹⁸ O isotopes. Both SIMS and nanoSIMS revealed the formation of a duplex oxide layer, consisting of an outer layer formed by outward Co cation diffusion and an inner layer growing by inward oxygen penetration, particularly in the grain-boundary regions of the outer oxide layer. The alloy is proposed to oxidise according to the Available Space Model.

A method is developed to exploit data on complex materials behaviors that are impossible to tackle by conventional machine learning tools. A pairwise comparison algorithm is used to assess a particular property among a group of different alloys tested simultaneously in identical conditions. Even though such characteristics can be evaluated differently across teams, if a series of the same alloys are analyzed among two or more studies, it is feasible to infer an overall ranking among materials. The obtained ranking is later fitted with respect to the alloy’s composition by a Gaussian process. The predictive power of the method is demonstrated in the case of the resistance of metallic materials to molten salt corrosion and wear. In this case, the method is applied to the design of wear-resistant hard-facing alloys by also associating it with a combinatorial optimization of their composition by a multi-objective genetic algorithm. New alloys are selected and fabricated, and their experimental behavior is compared to that of concurrent materials. This generic method can therefore be applied to model other complex material properties—such as environmental resistance, contact properties, or processability—and to design alloys with improved performance.

This study provides a comprehensive investigation of the formation and behavior of a layer enriched in fission products encountered between the (U,Pu)O₂ fuel pellet and the cladding, designated as JOG (“Joint Oxyde Gaine” in French). Employing a multifaceted approach that combined thermodynamic calculations, experimental synthesis, and advanced characterization techniques, simulated JOG has been synthetized (without radioactive fission products). Using thermodynamic calculations with the TAF-ID database, the phase compositions in the JOG was assessed for various temperatures, pressures, and oxygen potential conditions, revealing insights into the environmental factors influencing JOG formation. Experimental simulation of the JOG composition, exposed to controlled conditions, confirmed the presence of key compounds such as Cs₂MoO₄, CsI, and PdTe, as evidenced by SEM, EDS, and XRD analyses. The results of the calculations highlighted notable differences in the nature of the phases constituting the JOG under varying pressure and oxygen potential conditions. At 873 K and oxygen partial pressure of 10^–4 bar, Cs₂MoO₄, Pd–Te, and a gas phase rich in tellurium and CsI were predominant, contrasting with the emergence of liquid phases at 70 bar. This study offered a comprehensive understanding of JOG microstructure, and highlighting the importance of accurate characterization for reactor safety. This information lays the foundations for future studies on the chemical interaction between the JOG and the steel cladding.

Molten salts have been used as heat transfer fluids since the middle of the 20th century. More recently, molten chloride salts have been studied for use in concentrated solar power plants or molten salt reactors. However, none of the materials studied to date has been able to withstand this highly corrosive environment without controlling the salt’s redox potential. The alumina-forming alloy was a promising option, as it has not yet been widely studied. To investigate this possibility, two iron-based alumina-forming alloys were corroded in NaCl-MgCl₂ eutectic at 600 °C for 500 h after being pre-oxidised to grow a protective layer of α-alumina on each alloy. A salt purification protocol based on salt electrolysis was implemented to ensure comparable and reproducible results. During immersion, alumina was transformed into MgAl₂O_4, as shown by FIB-SEM observation. Inter and intragranular corrosion were observed, with the formation of MgAl₂O₄ in the corroded zones. The nature of the oxides was explained by the predominance diagram. Intragranular corrosion was 2 µm deep, and intergranular corrosion 10 µm deep. Alumina formed at the bottom of the intergranular corrosion zones. The depth of intergranular corrosion is consistent with O diffusion control at the grain boundary.

The aim of this paper is to present methods for corrosion mitigation in molten salt environments. The corrosion of structural materials depends directly on the redox potential of the salt. When the redox potential of the salt is higher than the standard potentials of the elements constituting the structural materials, corrosion occurs. If the reverse is true, no corrosion is observed. Herein, a methodology for calculating the theoretical potential of a molten salt is provided and compared with experimental measurements. Three ways to mitigate corrosion by modifying the salt redox potential are proposed: (i) using a soluble/soluble redox system; (ii) using a potentiostatic method; and (iii) using an amphoteric compound such as UCl₃, TiCl₂, or TiCl₃. Immersion tests were conducted under the above conditions to validate the methodology.