nanoIndEx will determine personal exposure to MNMs and thoroughly investigate the possibilities of personal monitors and samplers. Those samplers and monitors, identified as suitable for assessing personal exposure to MNMs will be scrutinized in laboratory and field studies to study their accuracy and the comparability of the different samplers and monitors and to search for possible correlations between metrics. All samplers and monitors that qualified during the lab-studies will be used in field studies in at least ten different nanotechnology workplaces. These field surveys will provide information on the field applicability and comparability of the instruments and generate a large data set on personal exposure to MNMs that will be provided to existing exposure databases. The experiences from the laboratory and field studies will feed into standard operation procedures and guidance documents on the proper use of the monitors and samplers and for data evaluation. All these documents will be made publicly available and distributed to stakeholders as well as national and international harmonization and standardization activities.

The SURHYMI project aims at developing a sustainable and integrated approach for the synthesis of hybrid mesoporous films and membranes densely and homogeneously functionalized by polymers, designed as platform materials for the elaboration of micropollutant removal devices. The control of the textural and chemical properties of the supported films and membranes (pore diameter and topology, and functions (acid, basic, cyclodextrin) in the mesopores), will allow to evaluate their performances in the reversible sorption of anionic, cationic and hydrophobic micropollutants based on electrostatic interactions or host-guest complexes. Novel polyion complex micelles (PIC) as well as host-guest inclusion complex (InC) micelles will be evaluated for the first time for their ability to controllably form a variety of ordered mesostructures by the sol-gel route, first as powders by macroscopic precipitation and then as films and membranes by deposition-evaporation. PIC micelles will be formed by electrostatic complexation between double-hydrophilic block copolymers (DHBC) and oppositely charged polyions, auxiliaries of micellisation. Poly(acrylic acid) and poly(aminoethylacrylamide) based DHBCs will be synthesized by RAFT in acidic media in order to protect the chain-transfer agent. Then, they will be used as platform polymers for the preparation by amidation reactions of a range of new DHBCs with beta-cyclodextrin (CD). Polymers with beta-CD functionalities will enable the formation of inclusion complex micelles (InC) with ditopic/multitopic guest species, which will be studied as silica structuring agents. PIC and InC assemblies will be evaluated for the first time as structuring, functionalizing and porogenic agents of functional mesoporous supported films and membranes. The new methodology developed should allow the preparation of materials whose mesopores will be intrinsically functionalized in a homogeneous and dense way by the targeted and previously prepared functions. The films will be prepared by evaporation induced assembly (EISA process). Depositions will be performed first on dense substrates, then on porous substrates. The disassembly of PIC and InC will allow the elution of the micellisation auxiliaries and will reveal the intrinsic functionalization of the layers with the three types of functions, acid, basic, and CD. The porous textures, thicknesses, density profiles and permeability of the functional films will be characterized. The influence of these properties will be evaluated for the sorption of model micropollutants as a function of physicochemical parameters (pH, concentration, ionic strength). Four organic micropollutants (hydrophilic cationic and anionic, as well as hydrophobic) were selected to demonstrate the specific and reversible character of the sorption mechanism in hybrid mesoporous silica-based platform materials. The kinetics, reversibility and repeatability of the sorption process will be studied as well as the chemical and structural recyclability and aging of the adsorbent materials. These results will be transferred to supported membranes to evaluate their filtration performance, chemical and structural stability and the mechanical properties of the prepared membrane materials.

The objective of this basic research project is to develop a new strategy for the treatment of radioactive effluents based on the use of a porous functionalized support. This support would allow at the same time the separation of the RadioNucleide (RN) using a selective organic function, and their encapsulation after collapse of the porosity by a "soft" way (sol-gel, heating under stress, irradiation effect). This new concept would result in obtaining a primary wasteform matrix. Mesoporous silicas will be used as model support materials, because the nanometric size of their pores allows easy closure. Furthermore, the silica has a chemical composition close to high-level nuclear waste packaging materials (glass). This new so-called separation / conditioning strategy would constitute a significant simplification of the number of step, compared to "traditional" processes for the treatment of radioactive effluents. Such traditionnal processes usually require a concentration step of radioactivity (evaporation, precipitation, etc.), followed by of a embedding step. It could be adapted to any type of liquid effluents, aqueous or organic, containing radionuclides emitter alpha, beta, gamma. This process could be interesting for the treatment of effluents produced in nuclear installations (STEL ...), but also for the treatment of effluents from dismantling sites because of its compactness. In this project we will focus our study on the treatment of effluents containing actinides, which have a significant radiotoxicity linked to the alpha decays induced . This mode of disintegration could be beneficial for the collapse of the mesoporous structure , leading directly to a "primary wasteform matrix". The closure of the porosity under self-irradiation will therefore be particularly studied, with the realization of materials doped with short-life actinides (244Cm, 238Pu). Another innovative aspect of the AUTOMACT project will be the search and grafting of selective actinide ligands. For that, tributyl phosphate, which is used in the Purex process for the separation of uranium and plutonium, is a potential candidate. The purpose of this project is therefore to propose a new all-in-one RN separation / conditioning route using specific materials allowing both decontamination operations and their simple evolution towards a primary containment matrix.

The ANR MULTISEPAR project aims to model rare earth (lanthanide) separation processes used in hydrometallurgy and for recycling. More specifically, it will focus on the solvent phase of liquid-liquid extraction processes, the modelling of which being currently at a very early stage. The multi-scale approach will be based on three complementary levels of description. First, at the atomic level, molecular dynamics simulations will calculate the structure and speciation in these solvent phases. The molecular interaction potential that we will use here has recently been validated from ab initio simulations by comparison with spectroscopy experiments. An umbrella sampling methodology will calculate the forces between solutes. The purpose of this step will be both the determination of the physico-chemical ingredients required for solvent phase modelling and also the calculation of the mesoscopic properties used by the other more macroscopic description scales. In another level of descriptions, mesoscopic Brownian simulations will be performed to calculate the effects at greater distance. Based on molecular simulation data (effective interaction potential and mobilities), either Brownian dynamics simulations or Multiparticle Collision dynamics simulations will be used to access the largest scales. The solutes activity coefficients and the stability of the solvent phase can thus be calculated. At the dynamic level, solute transport (diffusion and electrical conductivity) as well as viscosity will also be studied because they drive many industrial processes. As both experiments and molecular simulations show that in some cases solutes decompose poorly into independent particles but rather form a continuous network of hydrophilic parts in the solvent phase, we will also propose a second mesoscopic model to describe these solvent phases, this time based on a microemulsion model. Using a Gaussian random field methodology, we will propose a code representing the Gibbs energy of the solvent phase, which will make it possible to predict both the structure and the extraction properties. The fundamental quantities of this level of description will be here the properties of curvature (spontaneous curvature and rigidity) due to the extractants which will be deduced from the molecular simulations. The study of extraction as a function of the concentrations in the aqueous phase and of the extractant concentration will validate this methodology. We believe that this calculation will be a success if this microemulsion model can represent extraction equilibria with a much smaller set of parameters than traditional models based on multiple chemical equilibria between species. Thus, this project on lanthanide extraction could lead to a model that will be implemented in chemical engineering codes describing this process. We hope that through this multiscale project and the extensive use of numerical computing resources a new image of extraction mechanism will emerge from molecular modelling and that it will be able to bridge the gap to the macroscopic descriptions of this method of separation chemistry.

Since asbestos was forbidden in France in 1997, no materials have replaced this mineral for high temperature applications in the range [500°C, 1000°C]. This is particularly true in the field of sealing technology. This project is focused on the development of high temperature (up to 900 °C) gaskets for nuclear and solar energy, space motors, oil refining chemistry. All theses industries needs gaskets systems applied to severe environments (high pressure and temperature). The aim of the project is to develop a process for making gaskets based on inorganic lamellar materials for high temperature applications where graphite is not usable. Severals inorganic materials can be used: phyllosilicates such as vermiculite, pyrophilite, saponite, sepiolite, xonolithe, and talc or boron nitride. We will develop a process to form a compact and impermeable material from a mineral powder based on lamellar and possibly exfoliated clay. This material should keep far superior sealing characteristics with leak rates lower than 10-4 sccm cm-1 at 900°C, and compressive stress of approximately 20 MPa. The gaskets will be formed through uniaxial pressing or by impregnation of a mineral powder in order to obtain a cohesive, airtight, and compact material. The first step of the process will consist in the preparation by sonochemistry of a powder with a controlled surface chemistry and particle size. In order to increase the formability, inorganic polymer additives bonding the aluminosilicates particles will be added. The porosity of the seal material will be decreased by adding oxides nanoparticles or other minerals such as glass or salts. The porous structure of the gaskets will be studied as a function of the temperature and pressure by nitrogen adsorption measurements at 77 K (BET specific surface area, pore size distribution), scanning electron microscopy (SEM), diffusion coefficient measurement (obtained by proton NMR), and density measurements. The structure and microstructure depending on P and T will be also studied in situ by X-ray and neutron small angle scattering and diffraction. The helium leak rates and elastic recovery will be tested in the pressure (P<20 MPa) and temperature range (T<900°C) for all the prepared gaskets. We will develop models to correlate the properties to the multi-scale structure. These models will be first developed on graphite materials and then applied to the new composite materials based on lamellar aluminosilicates. These models will enable to correlate the multi-scale structure of the gaskets to their properties calculated by numerical simulations of the elastic recovery and the leak rate at P and T chosen in the range of use. The models will predict the performance of use of the gaskets. Moreover, the models and numerical simulations will direct the research toward the most promising materials and lead the working-out process to tend to the optimised densification. At the end of the research work, we will propose an optimised seal material base on lamellar silicates with given physics and chemical characteristics: particle size distribution, chemical composition, surface chemistry, porous structure, etc... Then the research process will be transferred to an industrial pilot level by the Garlock Company to product real commercial gaskets.