Le présent travail visait à développer et à étudier une nouvelle méthode de fabrication des guides d'onde, « High Index Soft Proton Exchange » (HISoPE) , qui permet de réaliser des guides d'onde très confinés (dne = 0,1). Des caractérisations en génération d’harmonique localisée ont montré que les propriétés non linéaires de ces guides ne sont pas détruites mais les guides HISoPE réalisés sur coupe Z peuvent présenter des modes ayant des pertes élevées. Ces pertes peuvent être éliminés en utilisant des bains plus acides pour l’échange, mais cela implique des déformations plus importante dans les guides d'onde canal et la nature hybride des modes propageant. Dans le cadre du projet PhoXcry, nous avons essayé de réaliser un modulateur électro-optique très efficace en combinant des cristaux photoniques et des guides HISoPE sur coupe X. Dans les meilleurs guides d'onde fabriqués sur coupe X, les pertes à la propagation, expliquées par la nature hybride des modes sont de 1.75dB/cm, mais dans les guides d'ondes nanostructurés il n’a pas été possible d’identifier clairement une bande interdite photonique. HISoPE en combinaison avec l’échange inverse (Reverse Proton Exchange, RPE) a montré un grand potentiel pour la fabrication de guides d'onde enterrés. Dans une expérience de SHG et malgré des pertes élevées de 2dB/cm, nous avons pu estimer une efficacité de conversion de 160%/W*cm2. Un comportement du coupleur directionnel a été observé dans les guides d'onde enterrés fabriqué en raison d’une cinétique RPE différente dans les différentes parties du guide d'onde. Un développement ultérieur de la méthode HISoPE + RPE devrait permettre d'améliorer la qualité des guides enterrés. / The present work aimed to develop and to study a new method of waveguide fabrication, High Index Soft Proton Exchange (HISoPE), which allows realizing highly confining waveguides in LiNbO3 (dne=0.1). Characterizations by localized SHG experiments, showed that the nonlinear properties of the HISoPE waveguides are not destroyed, but modes with high propagation loss were observed for planar HISoPE waveguides on Z-cut wafers. These losses can be eliminated by performing the exchange in more acidic bath, but this results in more important deformations in channel waveguides and in the hybrid nature of the propagating modes. In the frame of the project PhoXcry, we tried to realize a highly efficient electro-optical modulator by combining photonic crystals and HISoPE waveguides on X-cut wafers of LiNbO3. The losses of the waveguides fabricated on X-cut, attributed to the hybrid nature of the propagating modes, were estimated to be around 1.75dB/cm. The nanostructured waveguides exhibited high losses and it was not possible to identify clear optical band gap. HISoPE in combination with reverse proton exchange (RPE) showed a great potential for buried waveguide fabrication. We used them in a SHG experiment and despite elevated losses of 2dB/cm, the conversion efficiency was estimated as high as 160%/W*cm2. A directional coupler behavior was observed in the buried waveguides due to different RPE kinetics in different parts of the waveguide. A further development of the HISoPE+RPE process will improve the quality of the buried waveguides.

Cette thèse réalisée dans le cadre des projets PIE CNRS AMELI-0Pt et AMEPlas et ANR AMADEUS a regroupé plusieurs entités autour de la thématique des piles à combustible : Dreux Agglomération puis l’Agence Innovation Made In Dreux (MID), le GREMI, le LACCO et initialement l’industriel MHS Equipment. L’objectif de ce travail est l’élaboration par voie plasma et l’optimisation d’électrodes de piles à combustible de type PEMFC et SAMFC dans le but d’obtenir de bonnes performances avec des charges de platine ultra faibles ou sans platine. Le projet a été organisé en quatre étapes : l’étude de la croissance simultanée de platine et de carbone co-pulvérisés par plasma, la dispersion optimale de quantités ultra faibles de catalyseur, le remplacement du platine par un alliage bimétallique à base de palladium, et le dépôt direct du catalyseur sur la membrane par plasma. En utilisant un faisceau synchrotron de rayons X (Synchrotron SOLEIL), en collaboration avec le CRMD, l’étude GISAXS des couches minces Pt-C co-pulvérisés a révélé l’organisation particulière du platine dans ce type de nanostructure. Ces couches minces Pt-C offrent d’excellentes performances (20 kW.gPt-1) avec des charges de platine ultra faibles. Des électrodes PdPt (5 %at Pt) faiblement chargées permettent d’atteindre de bonnes performances en PEMFC quasiment sans platine (12,5 kW.gPd-1 et 250 kW.gPt-1). L’étude de l’activité de catalyseurs PdAu vis-à-vis de l’oxydation du glycérol a révélé l’origine des effets synergiques du palladium et de l’or en milieu alcalin. Le dépôt plasma direct de platine associé ou non au dépôt de carbone sur membrane a été optimisé. Les performances obtenues avec des CCM (Catalyst Coated Membrane) plasma démontrent l’intérêt de ce type d’architecture. / This research work has been achieved in the context of the PIE CNRS AMELI-0Pt and AMEPlas and ANR AMADEUS projects and has gathered several entities around the Fuel Cell research: Dreux Agglomération and Agence Innovation Made In Dreux (MID), the French national research laboratories GREMI and LACCO and initially the company MHS Equipment. The project aims at developing and optimising fuel cell electrodes (anode and cathode) for PEMFC (Proton Exchange Membrane Fuel Cell) and SAMFC (Solide Alkaline Membrane Fuel Cell) entirely by plasma in order to reach effective performances with ultra low platinum loadings or none at all. The project was divided into four stages: the study of the simultaneous growth of platinum and carbon co-sputtered by plasma, the optimum dispersion of a very small amount of catalysts, the replacement of platinum by a palladium based bimetallic alloy, and the direct deposition of the catalyst on the polymer membrane by plasma sputtering. By using an X-ray synchrotron beam light source (SOLEIL Synchrotron), in collaboration with the CRMD, the GISAXS study of co-sputtered Pt-C thin films has revealed the particular organisation of platinum inside this type of nanostructure. These Pt-C thin films offer excellent performances (20 kW.cm-2) with ultra low platinum amounts. Low loaded PdPt (5 %at Pt) electrodes offered good performances almost without platinum (12,5 kW.gPd-1 et 250 kW.gPt-1). The study of the activity of PdAu catalysts (plasma sputtered) on the glycerol electro-oxidation revealed the origin of the synergistic effects of palladium and gold in an alkaline medium. The direct plasma deposition of platinum associated or not with carbon deposition on membrane has been optimised. The performances of the plasma prepared CCM (Catalyst Coated Membrane) demonstrate the potential of this type of architecture.

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My research goals are to synthesize new zwitterionic perfluorosulfonimide (PFSI) monomer/polymers. They are expected to replace traditionally used perfluorosulfonic acid (PFSA) polymers as the electrolyte in PEM fuel cells. For the PFSI monomer preparation, we designed a nine-step synthesis route. Thus far, I have successfully completed the synthesis of 4- (2-bromotetrafluoroethoxy)-benzenesulfonyl amide, 4-acetoxybenzenesulfonic acid sodium salt, and 4-chlorosulfonyl phenyl acetate. The coupling reaction of 4-(2-bromotetrafluoroethoxy)- benzenesulfonyl amide with 4-chlorosulfonyl phenyl acetate, was troublesome due to slow reaction kinetics and byproducts. Additionally, I did a methodology study for the homopolymerziation of the perfluoro 3(oxapent-4-ene) sulfonyl fluoride monomer. We compared the weight average molecular weight (Mw) of different reaction conditions. The best Mw was achieved when the polymerization was carried out for five days at 100 °C and150 psi with 2 wt % initiator and 5 g of monomer. All the compounds were characterized by melting point, GC-MS, GPC, FT-IR, and 13C/1H/19F NMR.

In this dissertation, I will present the various work I have accomplished in regards to the design, simulation, and fabrication of holovideo and holodeck display technology. This includes: 1) design and analysis of a wavelength division multiplexing LiNbO3 waveguide device, 2) loss characterization and reduction (by way of reverse proton exchange) 3) design of a curved, near-eye AR display, and 4) a basis for acoustic holodeck technology (meant to service a system built from our optical devices). All these accomplishments represent, in concert, a manifestation of LiNbO3's capacity to serve as the building material central to modern holovideo displays. It is my hope that many future technologies will be built using these waveguides as their base.

It is very promising to introduce diazonium moiety into Nafion monomer based Diazonium (Perfluoroalkyl) Arylsufonylimide (PFSI) monomers for further polymerization and chemical grafting onto carbon electrodes as innovative electrolyte materials in the Proton Exchange Membrane (PEM) fuel cells. The PFSI polymers, more proton conductive and stable at high temperatures, can dramatically increase the stability and lifetime of the PEM fuel cells, compared to widely used perfluorosulfuric acid (PFSA) polymers. This paper presents such a straightforward methodology to optimally construct a new nafion based diazonium PFSI monomer analogue, 2-diazonium 4-(trifluoromethyl) perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide II. New approaches have been investigated to dramatically increase the percent yield for another monomer I, 4-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide. The thermal stability of the two monomer analogues then have been measured and compared. Another monomer analogue, 4-diazonium-3-fluoro perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonylimide III, has been attempted and discussed.

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

Philosophiae Doctor - PhD / The widespread use of fossil energy has been most convenient to the world, while they also cause environmental pollution and global warming. Therefore, it is necessary to develop clean and renewable energy sources, among which, hydrogen is considered to be the most ideal choice, which forms the foundation of the hydrogen energy economy, and the research on hydrogen production and fuel cells involved in its production and utilization are naturally a vital research endeavor in the world. Electrocatalysts are one of the key materials for proton exchange member fuel cells (PEMFCs) and water splitting. The use of electrocatalysts can effectively reduce the reaction energy barriers and improve the energy conversion efficiency.

Proton-Exchange Membrane Fuel Cells are an alternative source of electricity generation for automobiles and stationary power plants. With increasing concerns on environmental issues, recent research has focused on maximizing the efficiency and durability as well as minimizing the costs of fuel cells. One of the main areas of research is optimizing the structure of the cathode catalyst layer. The main driving force of this thesis was the effective visualization of nanostructure of the ionomer, which is responsible for proton conduction in the cathode catalyst layer. However, challenges regarding sample preparation and radiation damage still need to be well understood. Different sample preparation techniques of catalyst inks and catalyst coated membranes were used for Scanning and Transmission Electron Microscopy, such as freeze fracturing, ultramicrotomy and Focused Ion Beam. Comparisons of the microstructure and chemical differences of all components, especially the ionomer, prepared by ultramicrotomy and Focused Ion Beam, was done with Transmission Electron Microscopy and Scanning Transmission X-ray Microscopy applied to the same catalyst coated membrane sample. Detailed spectroscopic information regarding components in both specimens was compared with C 1s and F 1s near edge X-ray absorption spectra recorded in a Scanning Transmission X-ray Microscope. Focused Ion Beam causes extensive damage to the carbon support and ionomer but prepares thinner sections than ultramicrotomy. This work makes it possible to understand the limitations of each sample preparation and compositional analysis technique in order to later apply one of them to image the ionomer in the catalyst layer at the nanoscale, hopefully using tomography techniques. / Thesis / Master of Materials Science and Engineering (MMatSE)

Indiana University-Purdue University Indianapolis (IUPUI) / Proton exchange membrane fuel cells (PEMFC’s) offer an attractive alternative energy resource over traditional fossil fuels. The advantages such as high power density, relatively quick start-up, rapid response to varying loads and low operating temperatures make it a preferred technology option compared to other alternative energy sources. Nafion® by DuPont plays an integral role in the success of PEM fuel cells due to its high proton conductivity and high chemical and thermal stability. This research project aims to study the effect of mechanical and hygro-thermal stresses on the mechanical performance and proton conductivity of the membrane by subjecting it to realistic operating conditions such as those encountered in an automobile. In this thesis, the time-dependent behavior of the membrane has been modeled using a Prony series and the change in the conductivity due to mechanical loading was experimentally measured. The modeling of both electrochemical and mechanical properties can further be used in studying the degradation properties of the membrane and should guide the development of better membrane materials. Visco-elastic stress relaxation theory has been used in modeling the time-dependent behavior of the specimen. The EIS spectrum has been analyzed using a non-linear least squares method and an equivalent circuit method was also used to fit the spectra. This project was conducted in three phases. In the first phase a novel test facility was built to perform the experiments. A conductivity measurement test cell that measured the proton conductivity of a membrane was modeled and manufactured. The second phase included the design of different experiments that helped in modeling the interdependence of electrochemical and mechanical properties of the membrane. In this process, three series of experiments that tested the electrochemical and mechanical properties of the specimen were conducted. The membrane was held at constant strain and the through plane impedance was measured at different times during the test, specifically before and after stretching at ambient and varying environmental conditions. The membrane was also subjected to both mechanical and hygro-thermal loading conditions during the test. In the third phase, time-dependant mathematical model for the changes in the material properties were developed. The experimental apparatus thus tested the mechanical and electrochemical properties of the membrane simultaneously while the specimen was being subjected to constant mechanical and varying hygro-thermal conditions. Since the testing method is a novel procedure, the reliability and repeatability of the experimental facility has been verified before conducting the experiments. The experimental apparatus can further be used to test the membrane at varying strain rates and different hygro-thermal loading conditions in a consistent manner. The model developed can be used to analyze the degradation behavior of membrane and also to build better fabrication methods and membrane materials in future.