The emission of NOx - nitrogen monoxide (NO) and nitrogen dioxide (NO2) - by engines in a confined work environment without ventilation and exhaust treatments represents major health and safety issues. In France, almost 800,000 workers are exposed to such highly toxic NOx emissions. The NOA project aims to develop a NOx adsorption process for non-road vehicles using an optimal adsorbent. It will be loaded and transportable by the worker, to be placed at the exhaust gas outlet of vehicles. The adsorption cartridge needs then to be periodically changed since it works on an accumulative mode, by gas-solid adsorption. The regeneration of the process will therefore take place in time and deported from the vehicle. The operation chosen is the gas-solid adsorption which is more effective than the catalysis at low temperature. Technical obstacles exist; the proposed process has to be selective: to trap NOx without adsorbing water and carbon dioxide, and the affinity of the trapping materials with NOx has not to be too high to allow the regeneration. Therefore, a selection of materials (MOF, zeolites,) with properties required will be made thanks to DFT and GCMC calculations. The goal is to identify the best adsorbents with the highest affinity and largest uptake to NOx in the presence of H2O and CO2. The most promising adsorbents will be synthesized with different morphologies and characterized. A first principle model based on momentum, heat and mass balances will be developed in order to accurately predict the NOx concentration profiles over time at the outlet of a column containing the best adsorbents. Finally, calculations and experiments will be carried out to sizing and design of a transportable device. A technology transfer to companies for its development will be performed at the end of the project. These different activities are not time-sequential but fully interwoven throughout the development stages and the validation of the innovative concepts. The work program is divided into seven work packages (WP) over the 48 months, each WP comprising from 1 to 5 tasks. Five French teams are involved in this project: four academics and one private association (coordinator). The consortium is complementary; it combines the advantages of a multidisciplinary research, involving chemistry of materials, thermodynamic and kinetic analyses, multiscale modelling (molecular simulations and process simulations), process and chemical engineering applications with efficient synergies. It should identify the most promising adsorbents for a highly challenging targeted selective adsorption, and intends to develop industrial tools for occupational risk prevention and environmental protection. Technology transfer to companies for the development and commercialisation of the optimised material(s) and selected process will be dealt with by the coordinator. The NOA project contains an important part of experimental/modelling investigations. Therefore, it requires the recruitment of scientists as follows: two PhD students, one post-doc (18 months) and one master2 student (6 months). It requires also the purchase of manometry equipment for corrosive gas to carry out adsorption isotherms. The project has no rental costs. It does not request funding for the costs of acquiring licenses, patents, copyrights, etc. A consortium agreement will be established between the five partners in the first year of the project. The financial support requested for NOA project stands at 535 k€ for four years, and at 131 man-months (permanent staff). The scientific impact of the work will appear at various levels, with the three following objectives: (i) sharing research results with the scientific community (conferences, publications, etc) (ii) ensuring a wide awareness of the project to both potential end-users and to the general audience (technology transfer) and (iii) disseminating knowledge to people outside of the consortium through training activities.

The TNT-Sensor-IA project aims in designing of a new generation of multiplexed array microsensors integrating a metamaterials whose porosity can be spatially programmed. Such a direct laser writing approach associates the latest advances in multiphoton stereolithography (SLA) with those in the artificial intelligence. A progressive sensor specialization processing based on deep learning methods will be performed in order to detect TNT (2,4,6-trinitrotoluene) traces in complex gas mixtures. Note that the majority of the sensors use machine learning only through a unidirectional procedure that provides a simple feed back analysis of the sensor performance. The originality of our project is to propose an iterative algorithmic strategy to reprogram the sensor after each learning cycle. This advantage stems from the computational flexibility proposed by SLA to reprogram on demand the porosity of this metamaterial over a wide space of possible configurations. Hence, beyond the strategic issue to target TNT, the principal constituent of 85 % of unexploded land mines worldwide, the great ability of our multiplexed sensors for learning make them very promising candidates for other sensing applications.

Emulsion radical polymerization processes have created considerable wealth in many industrial sectors, including coatings, adhesives, paints, additives for textiles and paper… Traditionally, waterborne polymer dispersions are produced in stirred tank reactors by the thermally-activated free-radical polymerization of a starting monomer emulsion. The objective of this project is to exploit UV radiation to promote the formation of high solid contents polymer latexes. The breakthrough is to generate highly concentrated dispersions of monomer nanodroplets (< 100 nm), that are subsequently photopolymerized in a specially designed photochemical reactor to produce polymer nanoparticles. Replacing a thermal process by a photochemical one has several advantages: (i) UV irradiation can induce very high rates of initiation that directly affect the overall rate of polymerization. In fact, the radical generation is known to be controlled by the incident photon flux and by the absorption conditions of the reaction system inside the photochemical reactor. Remaining within the nanometric (submicrometric) size range, the ratio of light absorption vs. scattering will be optimized in order to work under best conditions as far as light penetration is concerned. (ii) Photopolymerization will favour the implementation of continuous processes replacing the production limiting semi-batch operations used nowadays in industry. (iii) Photochemically initiated radical polymerizations are generally temperature independent and bear a much higher potential of application due to defined solubility, emulsion stabilization and controlled polymerization kinetics. (iv) A photochemical technology also complies with impeding European directives on solvent emissions and energy reductions. A viable emulsion photopolymerization process can thus impart a wide range of attractive advantages of process intensification, but there is currently no mature technology in this field. To achieve this objective, the PHOTOEMULSION project will integrate contributions from two academic laboratories and an industrial partner: the Laboratoire de Photochimie et d'Ingénierie Macromoléculaires (LPIM, Université of Haute Alsace, Mulhouse), the Laboratoire des Interactions Moléculaires et Réactivité Chimique et Photochimique (IMRCP, Université Paul Sabatier, Toulouse III) and the MÄDER group. The LPIM (ex-Department of Phochemistry) is internationally recognized in the development of radiation-curing technology while the IMRCP has a complementary expertise in the domains of photochemical technology and engineering. A major change from the initial project submitted in 2010 is the involvement of MÄDER, responsible for planning and upscaling process innovations. MÄDER has a well-established activity in the sector of industrial and decorative coatings, and has been a pioneer company in the design and use of water-based paints and bio-sourced resins/monomers. As a result of the project, an innovative photopolymerization process in water will be introduced and applied in the highly technical market segment of bio-sourced latexes.

The project aims at growing germanene, the germanium equivalent of graphene, and study the physics of Dirac fermions in this two-dimensional (2D) material. Indeed, germanene departs from conventional 2D electrons systems and graphene by a buckled atomic structure and a significant spin orbit coupling. It should thus form a rich playground for fundamental studies in low-dimensional physics. Based on the expertise recently gained with the growth of germanene on Al(111) by partners of this project, we want to explore the growth of van der Waals heterostructures, consisting of germanene and 2D layered materials, that allow to minimize the interaction between germanene and these supporting materials. For that purpose, our consortium will rely on state of the art in depth characterization tools at the nanoscale: synchrotron radiation, scanning probe microscopy at low temperature with multiple tips and time-resolved spectroscopy capability. Our analysis based on versatile multi-physical characterization will be compared with calculations performed in the framework of the density functional theory, highlighting the impact of the atomic arrangement on the band structure of germanene and how the nature of the substrate might perturb the structural and electronic properties of this remarkable sheet of Ge atoms. Relevant to this project will be the measurement of the Dirac cone hallmark, the band gap, the carrier mobility and the charge transfer from the underlying layer. Also, we will strive to demonstrate the existence of the quantum spin Hall effect, that is expected due to the substantial spin-orbit coupling in germanene. Of particular interest is the study of defects and lattice deformations, that opens the door to topological transitions, like the Kekulé distortion, causing the attachment of mass to Dirac Fermions. Because of the anticipated poor resistance of germanene to ambient conditions, what would severely limit a deeper characterization and prevent its use in spin/opto-electronic applications, efforts will also be devoted to encapsulate germanene. We want to achieve the growth of germanene on Al(111) ultra-thin films on silicon, followed by the removal of the Si parent substrate and the oxidation of the Al layer, and, to protect the top face of germanene with 2D layered materials transferred in ultra-high vacuum. These schemes will take place along with innovations in instrumentations, in particular Raman spectroscopy in ultra-high vacuum that is the tool of choice for fingerprinting 2D materials. French companies that are involved in the Equipex and Labex investment awards of two of the partners will benefit from transfers of know-how in advanced instrumentations. Progress in the field of the synthesis of germanene, in the understanding of the physics of this material and in the design of dedicated tools will be key to turn germanene into practical technologies at the end of the project.