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).
Design of new extractant molecules for uranium and plutonium separation
The subject of this postoctoral position is related to the optimization of the process used to separate uranium and plutonium from spent nuclear fuels. In the so called PUREX process currently in operation at La Hague reprocessing plant in France, the TBP (tri-n-butylphosphate) is used as extractant in the solvent extraction system. This molecule shows high affinity for uranium and plutonium at oxidation states VI and IV and allows to reach high decontamination factors versus fission products. Nevertheless, the separation of U from Pu requires the use of reducing and anti-nitrous reagents to allow the back-extraction of Pu(III). In order to improve the process, researches are under way to design new extractant molecules which would allow to separate U and Pu without redox chemistry and with high selectivity versus fission products (Ru, Tc, Cs, lanthanides, etc) and other actinides (especially Np). The objective of the postdoctoral associate will be to select the molecules, to determine synthesis routes and to perform their synthesis using equipment available in the LCPE laboratory (micro-wave, flash chromatography, NMR, HPLC-MS, GC-HRMS) at the CEA Marcoule.
Improvement of microfluidic tools for kinetic data measurement
The development and modeling chemical processes require the acquisition of many thermodynamic and kinetic data . Conventional methods for measuring these data generally involve significant amounts of reagents. In particular for the reactive crystallisation, where the stochastic nature of nucleation requires the realization of a large number of experiments . The subject is to continue the work already done on the development of a dedicated chip to measure rapid nucleation kinetics . Firstly , the validity of kinetic measurements obtained by microfluidics technique will be evaluated and optimized based on well known and non- radioactive chemical systems . The microfluidic tool will then be used to study the sensitivity of these reactions to various operating parameters ( supersaturation , impurities , additives, etc. . ), before considering its transposition to nuclear processes such as decontamination of radioactive effluents. Finally, a new chip design could be proposed for the measurement of kinetics of liquid-liquid extraction , in connection with the development of new hydrometallurgical processes.
Development of methods for U quantification in cells after exposure to uranium
This project fits into the transverse Toxicology Program, led by CEA, whose purpose is to address by multidisciplinary approaches, the potential effects on living organisms of elements of strategic interest to the CEA. The objective is to provide some understanding on the mechanisms of uranium toxicity and behavior, in connection with its speciation in cells. Indeed, the radionuclides speciation governs their bioavailability, accumulation, biodistribution, toxicity, detoxification mechanisms and their interaction at the molecular level.
The post-doctoral project (12 months) consists in:
- Developing methods to quantify U accumulated in the cells as well as endogenous content of trace elements after exposure of cells to uranium.
- Developing methods to determine the precise isotopic composition of U in the cells after their exposure.
The candidate will be in charge of developing chemical purification and measurement methods for precise elemental and isotopic analyses. The analyses will be performed using inductively coupled plasma quadrupole mass spectrometer (ICP- MS Q) or inductively coupled plasma multi- collection mass spectrometer of the latest generation (ICP- MS MC), to achieve the lowest level of uncertainties.
Carbon nanotubes grafting for positive electrodes of lithium/sulfur cells
In a view to develop electric vehicles, researches on lithium batteries are now focusing on sulfur active material. Indeed, this new system should allow to produce cheap and high energy batteries of about 600 Wh/kg. While being developed for more than 40 years, the limitations of such a system are still quite problematic: elemental sulfur is an electronic insulator, sulfur and intermediate lithium polysulfides are soluble in the electrolyte and final discharge product Li2S is non-soluble and insulating too.
This post-doctoral position will thus aim at improving the performances of the sulfur positive electrode, by combining :
- Carbon nanotubes that will allow to improve the electronic conductivity of the positive electrode, as well as to provide a substrate for sulfur grafting
- Disulfide functions that will be grafted on the nanotubes. Thanks to this chemical grafting of active material, the electrochemical reaction would occur without leading to sulfur and polysulfides dissolution, thus leading to higher capacity and cyclability along with lower self-discharge.
Immunotargeting of based-organic nanoparticles for clinical applications
The project aims to tailor-make based-organic nanocarrier enabling to target antibodies to increase the efficacy of therapy (more particularly mantle cell lymphoma) for clinical applications. Our group has developed a unique delivery system based on lipid nanoparticles for imaging and therapeutic purposes since the last 6 years. Based on this technology, the candidate will:
- optimize the targeting of specific ligands into organic nanoparticles (bioconjugate chemistry)
- optimize the encapsulation of drugs in the immunotargeted nanoparticles
- assess the physico-chemical characterization of all nanoparticles
- evaluate the binding affinity of doped and targeted nanoparticles
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.
Multiscale approach of f elements aqueous solutions modeling
A post-doctoral position is available for one year at CEA-Marcoule
The study will be the modeling of concentrated aqueous phases of heavy metal salts using both microscopic and mesoscopic modeling.
Separation processes for heavy metals recycling usually use liquid-liquid extraction with the transfer of ionic species from a concentrated aqueous phase to an organized organic phase.
This post-doctoral research subject relates to the chemical properties of these processes, and especially to the characterization of the aqueous phase using as accurate as possible models. The goal is to understand the various effects (solvation, electrostatic and van der waals forces, entropy…) influencing the structural and energetic properties of these solutions. A multi-scale approach will be used to study some systems of interest for both fundamental and industrial point of view, the aim being the characterization of these solutions from their molecular structure to their thermodynamic properties. The tools and the approach used here have to be be valid for separative chemistry overall.
This study aims at the chemical synthesis of infrared emitting nanocrystals for integration in LEDs.
These nanocrystals will be characterized by TEM, XRD, EDX, UV-vis, PL, NMR, FTIR. Formulation of colloidal solutions suitable for deposition via inkjet printing.
The candidate will work in the partner lab INAC/LEMOH