Synthesis and structural analysis of reference uranium minerals for the identification of uranium-bearing phases in mining environment by TRLFS.

In the frame of the collaborative project between the ICSM , CEA and Orano, a study is conducted in order to detect and identify minerals containing uranium (VI) by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS). This technique showed its efficiency in order to identify the presence of uranyl in natural assemblies through the probing of the local environment of uranium. However, it requires the establishment of a database from synthetic and natural samples fully characterized. Therefore, in order to achieve this goal, we intend to synthesis, and thoroughly characterize a variety of compounds containing uranyl groups within the crystal structure. We can cite the families of oxi-hydroxide, sulfate, and silicates based compounds. Then, TRLFS spectra will be collected in order to complete the database and to evidence the impact of the local structure of uranyl cation on the intensity and the position of the emission bands. The obtained data will be also compared to a collection of natural samples.

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).

Synthesis of inorganic monoliths functionalized with nanoparticles

Since 2008, the "Institut de Chimie Separative de Marcoule" (ICSM) and specifically the "Laboratoire des Nanomateriaux pour l’Energie et le Recyclage" (LNER) has developped specific skills in synthesis routes and studies of porous materials (BET, TEM, SEM, SAXS).
This post-doctoral position is devoted to the synthesis of inorganic monoliths using high internal phase emulsion (HIPE) as soft template, and particularly to the functionalization of these materials with nanoparticles (NP).
The use of an emulsion in the procedure allows to consider innovative ways of functionalizing the material. For example, the oil-water interface in the emulsion may be the site of adsorption of nanoparticles of interest for a given application. In our case the goal is to prepare an emulsion with high internal phase (> 50% vol) stabilized by both surfactants (required for mesoporosity) and NP of interest to functionalize the macroporosity. NPs are chosen to cover liquid effluent decontamination (zeolite, nonatitanate, clathrate)

Synthesis and characterization of amino-phosphorous ligands for extraction of uranium in a sulfuric medium with a “liquid / liquid” process

The development of new and more effective extractants than those currently used is therefore an important issue for the mining of uranium. In particular, access to specific chelating systems with high affinity for uranium with selective properties in regards to competitor’s ions and less susceptible to hydrolysis remains a challenge.
Recently, new bifunctional molecules amio-phosphine oxide type has shown their potential for the extraction of uranyl in sulfuric media with excellent properties in terms of affinity and selectivity for the metal.
The objective of this postdoctoral fellowship will be to optimize this family of ligands, with the development of concise and efficient routes for their chemical and suitable for the preparation of large quantities of extractant for further study the optimization of the process.