Role of metal containers on the alteration of high-level waste confinement glasses in geological storage conditions: glass-iron interactions in hydrogen-tight reactors

Vitrified waste resulting from nuclear power plant fuel reprocessing, as well as their steel containers and overpacks, are intended for permanent storage in deep geological layers. Water will be the vector of glass alteration and potential migration of radioactive elements. The most advanced storage concept to date provides for the glass package to be protected for its thermal decay step from interaction with water by an unalloyed steel overpack. However, whether in the form of metallic iron or corrosion products of steels (oxides, carbonates, sulfides), iron plays a significant role in glass alteration.
The objective of this work is to understand and quantify the mechanisms of glass-iron interaction in order to strengthen the operational models for waste package performance. To this end, a bench of ten hydrogen-tight instrumented reactors has been developed in the laboratory. It has allowed the implementation of a first series of long-term experiments of several months, which concerned a non-radioactive model glass and a iron carbonate. The objective will be to carry out these interaction experiments using metallic iron this time, to characterize the sampled solutions and neoformed alteration products, and to interpret the experiments using the modeling tools available in the laboratory.

Behavior of materials in molten salts

Access to clean and affordable Energy is a key challenge in the current context of climate emergency. Several leads have been considered for several years but technological issues remain up to date to make it happen. From concentrated solar plant to 4th generation of nuclear reactor, molten salt is a promising media (both for heat transfer fluid and the fuel itself). Nevertheless, due to the presence of impurities, molten salts are highly corrosive for commonly used materials.
Most of the commercial alloys - either nickel based or iron base - seems to suffer from rapid attack. It is then needed to broaden the scope of the studies by investigating innovative materials. Thus, a screening of materials is planned to select the most interesting ones. After a thorough filtering, a study of the corrosion mechanism will be carried out through analysis at different scales (SEM, DRX, SDL, ICP, etc … )as well via electrochemical techniques and thermodynamic modelisation (HSC and FactSage).
The aim of the post doctoral subject offered at the S2CM (Service of corrosion and Behavior of Materials) consists in the entire study of the behavior, from the sample preparation to the caracterization of corrosion products. This topic is highly experimental and goes deep in the understanding of the corrosion mechanisms. This post doc position is part of a project gathering top - Notch industrial and academics (EDF,Framatome, Orano and the CNRS). Results obtained are subject to be presented to the different partners.

Design of a crystal growth process

Laser fusion facilities, like LMJ, require the use of large optical components. Some of them are large KDP or DKDP (KDP partially deuterated) plates extracted from single crystals.
Currently, DKDP single crystals are produced a by slow growth method were the growth time exceeds two years.
Here, we proposed to study a rapid growth method to reducing the growth time to a few months.

Improvement by thermodynamic calculations of the modeling for the joint oxyde-gaine and the fuel cladding chemical interaction into the fuel performance code GERMINAL

This work is proposed in the frame of studies on the physico-chemical behaviour of the (U,Pu)O2 fuel during irradiation considered for the future reactors of 4th generation. Indeed, this kind of fuel is subject in particular to two specific specific phenomena that can have an impact on its behaviour:
- the formation of a JOG (Joint Oxyde-Gaine), a fission products layer localised between the external surface of the fuel pellet and the inner surface of the cladding material ;
- the FCCI (Fuel-Cladding Chemical Interaction), which leads to the formation of a corrosion layer on the internal surface of the clad containing fission products and elements constituting the cladding material.
The goal is this work is to improve the modelling of the JOG and of the FCCI into the fuel performance code (FPC) GERMINAL, dedicated dedicated to the calculation of the thermo-mechanical and physico-chemical behaviour of fast reactor fuel irradiated in normal and off-normal conditions. For that purpose, the candidate will work on the dedicated calculation scheme of GERMINAL which uses the thermochemical software OpenCalphad and on the comparison of the JOG and of the internal cladding corrosion widths obtained to experimental observations obtained for some irradiation experiments. Complementary stand-alone thermodynamic calculations will be performed with the TAFID, thermodynamic database on nuclear materials developed in an international framework, in order to analyse the thermochemistry JOG/FCCI versus parameters of interest.
This work will be performed in collaboration with a team specialised in thermodynamic modelling, in charge of the TAFID project. The student will thus have the opportunity to exchange on his results in a collaborative frame with international partners. In addition, he will be able to highlight his work through publications and presentations at conferences.

Implementation of a sensor allowing the online monitoring of the corrosion of stainless steels in a hot and concentrated nitric acid medium

The control of materials (mainly stainless steel) aging of the spent nuclear fuel reprocessing plant is the subject of permanent attention. Some installations at La Hague plant will have to be replaced very soon. In this context, it is important for the industry to develop sensors that are resistant to concentrated nitric acid (˜ 2.5 mol / L) and temperature (from ambient to 130 °C), allowing the online monitoring of the corrosion.
The aim of this work is to manufacture one sensor for the detection of corrosion of the steel intended for handling by the operators of the plant. In case of a positive response, the second sensor is used.
The challenges of this work are essentially technological since it will develop or use materials adapted to concentrated and hot nitric acid media.
The laboratory is specialized in the corrosion study in extreme conditions. It is composed of a very dynamic and motivated scientific team.

Phenomenology of in-liquid plasma interactions applied to laser target manufacturing

Optical sensor development for in-situ and operando Li-ion battery monitoring

To improve the battery management system, it is required to have a better knowledge of the physical and chemical phenomena inside the cells. The next generation of cells will integrate sensors for deepest monitoring of the cell to improve the performances, safety, reliability and lifetime of the battery packs. The main challenge is thus to measure relevant physico-chemical parameters in the heart of the cell to get a direct access to the real state of the cell and thus to optimize its management. To address this challenge, a research project will start at CEA at the beginning of 2020 to develop innovative optical sensors for Li-ion battery monitoring. He / She will participate, in a first step, to the development of optical probes and their integration on optical fibres. The work will focus on the synthesis of a photo-chemical probe (nanoparticle and/or molecule) as active part of the sensor. Then, theses probes will be put on the optical fibre surface to form the sensor. The candidate will also participate to the realization of an optical bench dedicated to the testing of the sensors. In a second step, he / she will work on integrating the sensors into the Li-ion cells and test them in different conditions. The objective is to demonstrate the proof of concept: validation of the sensors efficiency to capture the behaviour of the cell and correlate it to electrochemical measurements.

Nanostructured negative electrodes for magnesium-ion batteries

The subject is part of an ANR project on the development of negative electrodes for magnesium (Mg)-ion batteries. Magnesium is an excellent alternative to lithium due to its high specific capacity, low cost, abundance on Earth and low reactivity. However, conventional electrolytes interact strongly with metallic magnesium to form a blocking layer on the surface of metallic Mg, inhibiting reversible electrochemical reactions. An interesting solution to overcome this problem is to replace the Mg metal electrode with a material compatible with electrolyte solutions having a large electrochemical stability window. Interestingly, Mg alloy compounds have adequate stability in conventional electrolytes, slightly higher potentials than pure metallic Mg with however lower specific capacities than Mg. As part of an ANR project, the LEEL laboratory develops new alloy compounds for Mg batteries in the form of nanostructured electrodes to overcome volume expansion and slow diffusion of ions during the alloying with Mg.
In this project, the postdoctoral associate will first be in charge of the fundamental understanding of the reactivity towards the electrolyte of the alloys developed in the laboratory, notably through impedance spectroscopy and XPS. Secondly, the postdoctoral associate will deal with the electrode and electrolyte formulation’s optimization with a systematic comparison of electrochemical performances in half-cell. Finally, full Mg-ion cells will be made with the better electrode/electrolyte combination.

Structural characterization, reactivity and physico-chemical properties of Pu(IV) colloidal suspensions

Pu(IV) is known to be highly prone to hydrolysis leading to the formation of extremely stable Pu(IV) colloidal suspensions (known as intrinsic colloids). The lack of knowledge concerning the speciation and reactivity of these Pu colloids hinders the development of reliable models allowing to predict their behavior in industrial and environmental systems. The behavior of these colloidal species towards dissolution, complexation, or aggregation has been very poorly described in the literature. It thus appears essential to study and characterize Pu(IV) colloids and in particular their surface charge properties which ensure their stability and their interactions with their environment. This pioneering project in the nuclear field aims to study and characterize colloidal Pu(IV) suspensions whose size, concentration and dispersion medium can be controlled by our approaches. It comprises: (i) the preparation of intrinsic Pu(IV) colloidal suspensions and the study of their chemical and sonochemical reactivity; (ii) the electrophoretic characterization of various colloidal suspensions and the study of their behavior under the influence of an electric field; (iii) the characterization of their multi-scale structural properties by small and large angle scattering (SAXS / WAXS) coupled with EXAFS / XANES measurements (MARS line, SOLEIL synchrotron).

Bio-compatible, bio-resorbable microbatteries for medical applications

In the framework of its activities dedicated to embedded micro-batteries, LETI initiates prospective research in the field of micro-batteries for medical applications, and in particular as energy power sources for implantable micro-devices. In this context, a collaborative project, including LETI labs and an academic Partner (ICMCB, Bordeaux), is aiming at designing, manufacturing and studying prototypes of bio-resorbable primary microbatteries.
The main tasks will include (i) a contribution to the design of the thin film electrochemical cell by the selection of adequate biocompatible materials (able to generate the targeted electrical power, corrodible and able to solubilize in the body), (ii) the manufacture of the cell constituents (electrodes, electrolyte, substrate) as thin films (sputtering, electrochemical plating, doctor blade coating) and their characterization,(iii) the achievement of full prototype cells and the study of their in vitro behaviour.
The work will be carried out at ICMCB (Bordeaux) in a joint CEA/ICMCB team, in collaboration with LETI labs in Grenoble.

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