HEALTHYGLASS will determine innovative, thermally activated chemical vapor deposition (CVD) processes of amorphous silicon oxide (SiO2) oxynitrides (SiOxNy) and oxycarbides (SiOxCy) on the internal surface of pharmaceutic vials, and will define their appropriate composition and structural characteristics in order to obtain efficient and sustainable barrier properties. The targeted function of these coatings is to limit the interaction between the stored drug and the glass vial, and thus allow to new advanced pharmaceutic molecules, especially in oncology, which are sensitive or aggressive towards the glass, to be commercialized. The generated innovation by the project in terms of materials solutions and deposition processes will thus allow pharmaceutic companies to dispose of high tech, chemical resistant vials, whose internal coating can be adapted to the characteristics of the stored drugs. There is limited information in the literature on the deposition of SiO2, SiOxNy and SiOxCy films with respect to the specifications defined by the project, namely atmospheric pressure and moderate deposition temperature (<570 °C), leading to dense and chemically inert films deposited on confined surfaces at high growth rate. The project team has recently tuned a deposition process of SiO2 at the internal surface of vials from mixtures of tetraethyl orthosilicate (TEOS) and oxygen. However, these films presented insufficient corrosion resistance in severe tests recommended by the US Pharmacopeia. In the frame of this project SiO2, SiOxNy and SiOxCy will be processed from TEOS and O3 based chemical systems including reactive compounds which activate radical mechanisms to enrich the films with nitrogen and carbon. CVD of SiO2 will be first investigated as starting point prior focusing on SiOxNy and SiOxCy which present remarkable barrier properties due to the densification of the network obtained from the partial replacement of O anions by highly coordinated N and C ones. State of the art protocols for the physico-chemical, structural and mechanical characterization, including microscopy, ellipsometry, nuclear and vibrational spectroscopies, atom probe tomography and nanomechanics tests, will provide information on these complex systems, including their surface and their interface with the glass substrate. The quantification of the connectivity of the silicate network, the structural disorder, the distortion of the Si environment, and the distribution of the oxynitrides and oxycarbide species will be monitored by solid state 29Si and 13C NMR, combined with XPS and µ-FTIR. High resolution 1H NMR and the very recent and challenging Dynamic Nuclear Polarization will reveal the hydrated species which are present on or by the surface. The hydrolytic resistance and the durability of the coatings will be evaluated by sterilization cycles preconized by the European and US Pharmacopeias. The most promising coatings will be tested in more severe conditions, e.g. ageing over a period of several weeks in basic and acid pH solutions. The releasing and corrosion mechanisms will be investigated and correlations among process conditions, structure and barrier properties will be established. HEALTHYGLASS will establish process/structure/properties/performance correlations which will lead to outstanding progress at fundamental level and will pave the way towards the application of these multifunctional and durable materials in complementary sectors concerned by the functionalization of complex surfaces such as micro- and nano-electronics, plastics, medical devices and implants, or gas sensors.

This project addresses the point 4.2 of the call for proposal, dedicated to electrochemical capacitors (ECs) so called supercapacitors or ultracapacitors. This point mentions that : « A major effort of research must focus on improving the energy density, including implementation of new organic electrolytes to increase the electrochemical window and security. Asymmetric or hybrid systems are other avenues to explore.”.Our goal is to double the energy density of nowadays symmetrical carbon ECs, i.e from 5 to 10 Wh/kg or 7 to 15 Wh/L. Unlike most of todays research efforts which aim at replacing carbon by other materials (oxides, nitrides, etc...), thus leading to drastic changes in fabrication process, we propose to keep the carbon electrode and simply add electroactive molecules that will be anchored at the surface of carbon, thus adding a faradic component to the double layer capacitance of carbon. This concept is not new since it has been developed for more than 5 years by the partners of this consortium as well as by other teams. However, most of the work has been done in aqueous based electrolytes. The Technology Readiness Level (TRL) is at stage 2 (Invention begins, practical applications can be invented, applications are speculative). Our goal is to apply the current knowledge to the development of devices in organic based electrolytes, and to push TRL level to stage 4 (Basic technological components are integrated to establish that they will work together), being able at the end of the project to give prototype cells to companies for initiating stage 5 of TRL (Component validation in relevant environment). Subsequently the present project is dedicated to technological developments. We want to improve the energy density of carbon-based devices in organic electrolyte by two fold. This will be achieved by keeping the same cell voltage (or slightly increasing it), almost the same double layer capacitance (EDLC) of carbon electrodes but providing an extra Faradaic capacity (and not capacitance since it is purely Faradaic) to both carbon electrodes by functionalizing the surface of carbon with judiciously chosen electroactive molecules. This concept has been successfully applied to aqueous based electrolyte using quinone based functionalized carbons. The choice of the electroactive molecules (multi-electron processes are preferred to single electron process, low molecular weight is needed, adequate active electrochemical window…), the choice of the carbon (large surface area, adequate porosity not too much affected by molecular grafting on the surface, etc…), the interaction between the molecules and carbon powder (high grafting yield, etc..) and finally the behavior of modified carbon electrodes in different organic (or ionic liquid) based electrolytes are the key points that control the final performance of the modified carbon electrodes. These requirements correspond to the 5 tasks of the project. Doubling the energy density must be achieved while keeping high power capability and long term cycling efficiency which are the bottlenecks of the proposed technology. For this purpose, a consortium gathering 4 academic laboratories (including a Canadian partner) has been set up. The 4 labs have been working together for more than 12 years with more than 30 common papers and communications and already 5 common PhD and post-docs. The consortium will take benefit from the belonging of the French labs to the French Network on Energy Storage (RS2E - http://www.energie-rs2e.com/fr) to get access to prototyping facilities to lead the concept to 1000F cells.

Through the Hydromore project, the original idea of an intensified heat exchange reactor is proposed for future industrial hydrogenation units. It consists in a monolith-type reactor offering parallel channels of mm scale, dedicated alternatively to the reaction and to the circulation of a cooling fluid. Ideally the monolith structure is made of a highly heat-conducting material (metal, silicon carbide). This new kind of multiphase monolith-type reactor will offer many advantages: good ability to reduce heat and mass transfer resistance, especially in the so-called Taylor flow (bubbles - slugs), which is crucial for fast exothermic reactions; convenience to high pressure and temperature; weak axial dispersion in the liquid phase, leading to better chemical conversion and to less wastes; laminar flow, allowing identification of data and test of catalysts; low pressure drop; safety for reactor operation (as the reactants cut-off leads to rapid reactor draining and stops the reaction). Important gains are then expected, thanks to the better control of mass transfer steps, heat removal, and temperature level. This new reactor will be applied to the hydrogenation of a bio-sourced olefin, alpha-pinene, and of an edible oil, sunflower oil (rich in linolenic and linoleic fatty acids, molecules to be hydrogenated for food conservation purpose). For the complete hydrogenation of the terpene, the reaction yield should be improved, inducing cost and energy savings for the further step of product separation. For the treatment of the edible oil, the selectivity of the reaction towards monoene and with respect to isomerisation reactions should be increased, so that the amount of unhealthy saturated trans fats in the hydrogenated products could be minimized. Some data and knowledge related to this project can be found in literature, upon which the project will lean: studies dedicated to monolith reactors and to catalyst optimization for hydrogenation reactions, models for gas-liquid mass transfer in Taylor flow. Some rare studies have tackled the question of heat evacuation in monoliths. The major barrier to the achievement of the project consists however in the coupling of phenomena that occur simultaneously inside the reactor (momentum, mass and heat transfers, diffusion, reaction); this coupling makes the control, modelling and design of the reactor complex. Another question that arises is the technical feasibility to coat with a catalytic layer the materials considered in this project for monolith walls (SiC…). To face these difficulties six partners will collaborate, with complementary competence fields: - the group Total-Fluides has developed a strong expertise in catalytic hydrogenation of fossil fluids through its four hydrotreating units of Oudalle (France), and is keen on industrializing a novel cutting edge process. - Deposition of washcoats of metal catalysts has been studied and applied to metal-made monoliths at the Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux (Toulouse). - Investigation and modelling of selective hydrogenation kinetics have been performed at the Laboratoire de Génie Chimique (Toulouse), as well as operation and dynamic modelling of fixed bed reactors. - A specific analytical technique for on-line and in situ measurements of vegetable oils composition has been developed at the Laboratoire de Chimie Agro-Industrielle (Toulouse). - Experimental measurement of local mass transfer fluxes near bubble caps and films in a tube has been successfully tested at LGC by means of a laser technique. - The numerical analysis of Taylor bubble flows in pipes and capillaries has been performed at the Laboratoire d’Ingénierie des Systèmes Biologiques et des Procédés (Toulouse). - The modelling of gas-solid exothermal reactions within monolith-type reactors has been achieved at Laval University (Canada). - Eco-design of products and processes has been performed at LCA.

We propose to design, to fabricate and to characterize All-Dielectric Metamaterials which rely on Mie resonances of high permittivity ceramic resonators for the terahertz frequency range. Then, we intend to realize all-dielectric metamaterial-based devices, especially, graded index lenses which would apply for biological imaging and spectroscopy in this frequency range. Our aim is to demonstrate that all-dielectric metamaterial are are suitable materials to construct devices (lenses, switches, modulators, etc.) operating in the THz range. Thus, this project is devoted to the micro-structuring of high permittivity ceramics resonators in order to highlight negative refractive index in the terahertz frequency range. For the sake, appropriate dielectrics materials have to be determined, whose complex relative permittivity have to be optimized and granularity to be on a nanometer scale. They will be synthesized as powders. From these, ceramics will be fabricated, shaped and micro-structured in order to ensure the requisite resonances. Then, the samples and the device will be characterized by the means of time domain terahertz spectroscopy.

Aging aircrafts are experiencing high level of maintenance costs to reduce the risk due to structural effect of existing corrosion damage for which the propagation rate cannot be predicted with a sufficient level of reliability. Indeed, in service, aircraft can suffer from cumulative corrosion and fatigue damage. Therefore, the evolution of corrosion in aluminium alloys, in particular the propagation of intergranular corrosion, remains not only a problem of fundamental interest but is also a key point in aircraft risk and reliability analysis as corrosion damage and mainly intergranular corrosion has a detrimental effect on integrity of aircraft structures by promoting fatigue crack initiation. The concept of M-SCOT is driven by the important need in developing strategies for validating engineering scale tests that would allow the detrimental effect of an intergranular corrosion defect to be evaluated and the remaining lifetime of the corroded structural parts to be quantified. In M-SCOT, it is proposed to revisit laboratory scale tests completed by micro-environmental scale simulations. To illustrate how the propagation rate of intergranular corrosion defects and therefore the validation of tests (at various scales) is strongly dependent of the role of the microstructure, M-SCOT project will be focused on the typical case of the propagation of the intergranular corrosion of AA2024 as it is largely described from the phenomenological point of view in literature and represents a significant cause of structural damage in ageing civilian and military aircrafts. The final scientific objective is to reduce the lack of predictive data for intergranular corrosion which is a bottleneck in implementation of operational management of existing defects in structures. The scientific and technical work plan has been defined to cover all the relevant scales for this type of corrosion to develop an engineering testing methodology based on a mechanistic (laboratory scale tests) and kinetic understanding of intergranular corrosion propagation rate (modelling at the microstructural scale). The key deliverables will be to predict quantitative estimations of the intergranular corrosion rate propagation on the basis of coherent results of tests (tests on specially designed specimens or using simulation based testing), conducted at microstructural scale in simulated environments, at laboratory scale in controlled environments and finally at engineering scale in standardized atmospheric environments (natural marine, salt spray, immersion-emersion exposures). It is planned to demonstrate that the prediction of the intergranular corrosion rate results from the benchmarking of the average and maximum penetration depths obtained from testing on metallic specimen compared to the instantaneous propagation rate defined from modelling. Beyond the immediate project, the final technical deliverable will be structured as an application guide which will helps engineers to improve and rationalize their knowledge on corrosion testing, to propose durable and damage tolerant designs. The engineering models developed will predict the performance of structural parts of aircrafts during service life. This demand is and will be more and more important as metallic materials (aluminium alloys) are and will be combined with composite materials by hybrid joining generating specific features of corrosion damages.