<p>Deep brain stimulation (DBS) electrodes are intended to stimulate specific areas of the brain to treat movement disorders including essential tremor, Parkinson's disease and dystonia. An important goal in the design of next generation DBS electrodes is to minimize the power needed to stimulate specific regions of the brain. A reduction in power consumption will prolong battery life and reduce the size of implanted pulse generator. Electrode geometry is one approach to increase the efficiency of neural stimulation and reduce the power required to produce the level of activation required for clinical efficacy. </p><p>We first characterized the impedance of the presently used clinical DBS electrodes <italic>in vitro</italic> and <italic>in vivo</italic>. Characterization of the electrode-tissue interface impedance is required to quantify the composition of charge transfer to the brain tissue. The composition of charge transfer was dependent on both the current density and the sinusoidal frequency. The assumption of the DBS electrode being ideally polarizable was not valid under clinical stimulating conditions. This implies that irreversible processes that can cause electrode or tissue damage might occur when high charge injection is required for DBS. </p><p>Current density distribution is an important factor in determining patterns of neural excitation, tissue damage and electrode corrosion. We developed a recursive simulation scheme to calculate the current density distribution that incorporates the nonlinear electrode-tissue interface into finite-element based models of electrodes. The current density distributions on the electrode surface were strongly dependent on the sinusoidal frequency. The primary current density distribution without including the electrode-tissue interface can be used to estimate neural excitation, tissue damage and electrode corrosion with rectangular stimulus pulses as most of the signal power is at frequencies where the secondary current density distribution matches closely the primary current density distribution.</p><p>We designed and analyzed novel electrode geometries to decrease stimulation thresholds, thus reducing power consumption of implanted stimulators. Our hypothesis was that high-perimeter electrode geometries that increase the variation of current density on the electrode surface will generate larger activating functions for surrounding neurons and thereby increase stimulation efficiency. We investigated three classes of electrodes: segmented cylindrical electrodes, serpentine-perimeter planar electrodes, and serpentine-perimeter cylindrical electrodes. An approach that combined finite element models of potentials and cable models of axonal excitation was used to quantify the stimulation efficiency of electrodes with various geometries. Increasing the electrode perimeter increased the electrode efficiency by decreasing stimulation threshold. Both segmentation and serpentine edges provided means to increase the efficiency of stimulation. Novel cylindrical electrodes that combined segmentation with serpentine edges decreased power consumption by ~20% for axons parallel to the electrode and by ~35% for axons perpendicular to the electrode. These electrode designs could potentially prolong the average battery life of deep brain stimulator by more than one year.</p> / Dissertation

The recent discovery of high-temperature superconductivity in Fe-based materials triggered worldwide efforts to investigate their fundamental properties. Despite a lot of similarities to cuprates and MgB2, important differences like near isotropic behaviour in contrast to cuprates and the peculiar pairing symmetry of the order parameter (OP) have been reported. The OP symmetry of Fe-based superconductors (FBS) was theoretically predicted to be of so-called s± state prior to various experimental works. Still, most of the experimental results favour the s± scenario; however, definitive evidence has not yet been reported. Although no clear understanding of the superconducting mechanisms yet exists, potential applications such as high-field magnets and Josephson devices have been explored. Indeed, a lot of reports about FBS tapes, wires, and even SQUIDs have been published to this date. In this thesis, the feasibility of high-field magnet applications of FBS is addressed by studying their transport properties, involving doped BaFe2As2 (Ba-122) and LnFeAs(O,F) [Ln=Sm and Nd]. Particularly, it is important to study physical properties in a sample form (i.e. thin films) that is close to the conditions found in applications. However, the realisation of epitaxial FBS thin films is not an easy undertaking. Recent success in growing epitaxial FBS thin films opens a new avenue to delve into transport critical current measurements. The information obtained through this research will be useful for exploring high-field magnet applications. This thesis consists of 7 chapters: Chapter 1 describes the motivation of this study, the basic background of superconductivity, and a brief summary of the thin film growth of FBS. Chapter 2 describes experimental methods employed in this study. Chapter 3 reports on the fabrication of Co-doped Ba-122 thin films on various substrates. Particular emphasis lies on the discovery of fluoride substrates to be beneficial for epitaxy without compromising superconducting properties. It is worth mentioning, that a world record Tc of 28 K for Co-doped Ba-122 thin films is reported here. Chapter 4 describes high-field transport properties (up to dc 35 T) of epitaxial P-doped Ba-122 thin films prepared by MBE. Among the FBS, P-doped Ba-122 shows very high transport critical current densities, although the Tc is lower than for LnFeAs(O,F)[Ln=Sm and Nd]. Additionally, the film is microstructurally clean. These high Jc values are due to a high vortex line energy. Chapter 5 deals with transport properties of epitaxial SmFeAs(O,F) thin films. In the course of this work, a dc 45 T magnet has been used within collaboration with the National High Magnetic Field Laboratory at Tallahassee, FL, USA. SmFeAs(O,F) thin films have been prepared by molecular beam epitaxy (MBE). The investigated film shows a very high transport critical current density (Jc) of over 105 A/cm2 at 45T and 4.2K for both main crystallographic directions, which features favourable for high-field magnet applications. Additionally, by investigating the pinning properties, a dimensional crossover between the superconducting coherence length and the FeAs interlayer distance at 30-40K was observed. Chapter 6 reports on high-field transport properties of NdFeAs(O,F) thin films prepared by MBE. In this case, the transition from Abrikosov to Josephson vortices was observed around 20-30K. Additionally, the angular Jc data were scaled with the anisotropic GinzburgLandau approach. The obtained parameters at given temperature are observed to increase with decreasing temperature, which is different from Co-doped Ba-122. Chapter 7 summarises this work. / Die kürzliche Entdeckung von Hochtemperatur-Supraleitung in Fe-basierten Materialien löste weltweite Bemühungen aus, deren grundlegende Eigenschaften zu untersuchen. Neben vielen Gemeinsamkeiten mit den Kupraten und MgB2 sind wichtige Unterschiede wie nahezu isotropes Verhalten (im Gegensatz zu den Kupraten) und eine auffällige Paarungssymmetrie des Ordnungsparameters (OP) berichtet worden. Die OP-Symmetrie der Fe-basierten Supraleiter (FBS) wurde theoretisch als s± berechnet, noch bevor experimentelle Versuche unternommen wurden. Derzeit favorisieren experimentelle Ergebnisse das s±-Szenario, dennoch gibt es noch keine definitiven Nachweise. Obwohl noch kein komplettes Verständnis des supraleitenden Mechanismus existiert, wurden schon potentielle Anwendungen wie Josephson-Elemente und Hochfeldmagnete erforscht. In der Tat erschienen zahlreiche Veröffentlichungen über supraleitende Kabel, Bänder und auch SQUIDs. Diese Arbeit befasst sich mit der Durchführbarkeit von Hochfeld-Anwendungen durch die Untersuchung der Transporteigenschaften von FBS, namentlich Ba-122 und LnFeAs(O,F)[Ln=Sm und Nd]. Es ist von großer Wichtigkeit, die physikalischen Eigenschaften in einer Probenform zu untersuchen, die der Form in Anwendungen nahekommt (z.B. Dünnschichten), um dieselben Rahmenbedingungen vorgeben zu können. Es ist jedoch nicht einfach, epitaktische FBS Dünnschichten zu realisieren. Kürzlich gewonnene Erkenntnisse in der Herstellung von epitaktischen FBS-Dünnschichten ermöglichen nun ein tieferes Eindringen in die Transporteigenschaften. Die in diesen Untersuchungen gewonnenen Informationen stellen somit wichtige Argumente in der Diskussion um Hochfeld Anwendungen dar. Diese Arbeit besteht aus sieben Kapiteln: Kapitel 1 beinhaltet die Motivation dieser Arbeit, die Grundlagen der Supraleitung und eine kurze Zusammenstellung der bisherigen Arbeiten zur Dünnschichtherstellung von FBS. Kapitel 2 beschreibt experimentelle Methoden, die im Zuge dieser Arbeit verwendet wurden. Kapitel 3 berichtet von der Herstellung Co-dotierter Ba-122 Dünnschichten (Co-Ba-122) auf verschiedenen Fluoridsubstraten. Dabei wurde Augenmerk darauf gelegt, neben einem verbesserten epitaktischen Wachstum der Dünnschichten die supraleitenden Eigenschaften nicht zu beeinträchtigen. Anzumerken ist, dass in diesem Rahmen Tc-Rekord-Werte von 28 K in Co-Ba-122 erzielt werden konnten. Kapitel 4 beschreibt die Hochfeld-Transporteigenschaften epitaktisch gewachsener P-dotierter Ba-122 Dünnschichten, die durch MBE hergestellt wurden. Unter den FBS zeigt P-dotiertes Ba-122 enorm hohe kritische Transport-Stromdichten, obwohl das Tc niedriger ist als bei LnFeAs(O,F)[Ln=Sm und Nd]. Der Grund dafür konnte in der hohen Flusslinienkern-Energie des P-dotierten Ba-122 ermittelt werden. Kapitel 5 behandelt Transporteigenschaften von epitaktisch gewachsenen SmFeAs(O,F)-Dünnschichten. In diesem Zusammenhang wurde ein dc-45 T-Hochfeldmagnet in Zusammenarbeit mit dem National High Magnetic Field Laboratory in Tallahassee, Florida, USA, genutzt. SmFeAs(O,F)-Dünnschichten wurden mit dem Molekularstrahl-Verfahren (MBE) hergestellt. Die Schichten zeigen sehr hohe kritische Transport-Stromdichten (Jc) von über 105 A/cm2 bei 45 T und 4.2 K für beide kristallographische Hauptrichtungen, parallel zur c-Achse und in der ab-Ebene. Diese Ergebnisse sehen sehr verheißungsvoll für eine Verwendung in Hochfeld-Anwendungen aus. Zusätzlich konnte durch die Untersuchung der Pinning-Eigenschaften ein Dimensionsübergang zwischen supraleitender Kohärenzlänge und FeAs-Ebenenabstand im Bereich 30-40 K beobachtet werden. Kapitel 6 berichtet über die Hochfeld-Transporteigenschaften von NdFeAs(O,F)-Dünnschichten, die mithilfe des MBE-Verfahrens hergestellt wurden. In diesem Falle konnte ein Ubergang von Abrikosov- zu Josephson-Flusslinien im Temperaturbereich 20-30 K beobachtet werden. Zusätzlich konnte die winkelabhängige kritische Stromdichte mit dem anisotropen Ginzburg-Landau-Ansatz skaliert werden. Die erhaltenen Parameter für verschiedene Temperaturen steigen mit fallender Temperatur. Dieses Verhalten ist gegensätzlich zu dem in Co-dotiertem Ba-122 gefundenen. Kapitel 7 gibt eine Zusammenfassung dieser Arbeit.

Detailed, accurate measurements of critical current density and resistivity to determine the upper critical field have been made on a technological NbsAl conductor in magnetic fields up to 15 T, temperatures from 4.2 K up to the critical temperature and in the strain range from -1.8% to 0.7%. The uncertainty in temperature above 4.2 K was equivalent to ± 100 mK with a stability during the measurements of < 5 mK up to a limiting current of 80 A and a typical noise level of 1 µ Vm(^-1).When B(_c2){T,ε) is defined at 5%pn, 50%pn or 95%/%pn, an empirical relation is found where and an approximate relation, holds. The Jε data were parameterised using F(_p) = J(_E)B = A(ε)[Bc(_2)](^n)b(^p)(1-b)(^9) where b = B/B(_c2)(T,ε). When B(_c2)(T,ε) is constrained to be the value at 50%pn or 95%pn, the scaling law for F(_p) breaks down such that p and q are strong functions of temperature and q is also a strong function of strain. However, when B(_c2)(T,ε) is defined at 5%pn, there is good scaling where p and q are constants independent of temperature and strain. F(_p) can also be approximated by a Kramer form where the Ginzburg-Landau constant is γ is the electronic density of states and is interpreted as the average B(_c2) for the bulk where percolative current flow occurs. The critical current density of Hot Isostatic Pressed (HIP'ed) and unHIP'ed Nb(_3)Sn Modified Jelly Roll wires has also been measured at 4.2 K. The critical current and upper critical field were decreased for the HIP'ed sample. The reduced upper critical field of the HIP'ed wire was found to be less sensitive to strain than the unHIP'ed wire. The exponent of B(_c2) in the flux pinning scaling law increased from 0.86 to 2.14 as a result of the HIP processing.

Ce travail porte sur l’analyse du comportement en durabilité d’une cellule à oxydes solides en fonctionnement en mode Electrolyse de la vapeur d’eau à Haute Température (EHT). Il s’agit plus particulièrement d’identifier les paramètres influant sur la durabilité de la cellule et de comprendre les mécanismes associés, de manière à établir le meilleur compromis durabilité-performance. Un premier axe de recherche correspond à la caractérisation électrochimique initiale de la mono-cellule choisie pour l’étude, à savoir une cellule à électrode support de type LSFC/YDC/8YSZ/Ni-YSZ dont le comportement électrochimique est étudié sous diverses températures, conditions de gaz et densités de courant. Ensuite, la dégradation des performances est étudiée in situ par spectroscopie d’impédance électrochimique et voltampérométrie lors de diverses études séquentielles par paliers de 200 heures. L’influence du taux de conversion et de la densité de courant sur la dégradation des performances est ainsi analysée. Pour compléter cette étude, des analyses physico-chimiques et microstructurales post tests ont été réalisées sur des échantillons ayant fonctionné 1000 heures afin de faire le lien entre les modifications électrochimiques observées et les changements de structure et de composition des matériaux de cellule. Des hypothèses de mécanismes de dégradation ont ainsi pu être formulées. / This work is dedicated to the study on the long term behavior of a solid oxide electrolysis cell (SOEC). More specifically, the target is to identify and understand the influence of main working parameters on the cell durability in order to find the best compromise between performances and durability. The initial part of this work is to characterize electrochemically the single cell selected for the study, that is to say a cathode supported cell of the type LSFC/YDC/8YSZ/Ni-YSZ at different gas conditions, temperature and current density. Then, the degradation of the cell performances has been studied by Electrochemical Impedance Spectroscopy (EIS) and voltamperometry (i-V) curves during sequential tests of 200h. The influence of the most important working parameters like the current density and the steam conversion has been analyzed. To complete this study, physico-chemical and microstructural analyses have been performed on cells that have been operated over 1000 hours, to make a link between electrochemical degradation observed on the cell and composition and structural changes of cell materials.

Ce travail a permis de développer une technique non invasive d’identification de la distribution du courant dans une pile à combustible à partir du champ magnétique externe. La mesure du champ s’effectue sur un ensemble de points de mesures choisis spécialement pour détecter les variations du champ par rapport à un fonctionnement optimal de la pile. Les deux composantes du champ magnétique sensibles aux variations sont utilisées. La mesure du champ exploitable est la différence entre un mode considéré sain et un mode quelconque de fonctionnement. Autour de ces mesures de champ magnétique, un problème inverse est modélisé en explorant plusieurs approches de paramétrisation de la distribution du courant. Le caractère mal posé du problème s’est traduit par la non-unicité de la solution et sa sensibilité au bruit. L’affranchissement de ces problèmes est atteint par la régularisation du modèle inverse. L’outil développé permis de reconstruire la distribution du courant indépendamment de la taille du défaut dans la limite de sensibilité. La validation est faite sur un simulateur électrique de pile à combustible et sur une pile de type GENEPAC dans un environnement de laboratoire. / A noninvasive technique for identifying the current distribution in a fuel cell from the external magnetic field is developed. The magnetic field measurements are carried out on a set of points chosen in order to detect only the variations of the magnetic field in a case of a faulty fuel cell. Two components of the magnetic field are used because they are sensitive to current heterogeneities. The exploitable measurement of the magnetic field is the difference between a healthy mode and a faulty mode.An ill-posed inverse problem is modeled by investigating several parametrization approaches of the current distribution. The ill-posed property of the problem conducts to a non-uniqueness of the solution and a high sensitivity to the noise. A regularization method is used in order to get a stable solution. The developed tool allows identifying the current distribution independently of the size of the fault within the sensitivity limit. A validation is done on a fuel cell simulator and on a GENEPAC fuel cell in a laboratory conditions.

Les piles à combustible à membrane échangeuse de protons (PEMFC) constituent une alternative aux moteurs thermiques utilisés dans le cadre d’applications transport ou dans le cadre d’applications stationnaires. Cependant, une large commercialisation des PEMFC dépend des progrès qui peuvent être réalisés pour améliorer leur fiabilité et leur durabilité. La PEMFC est sujette à plusieurs types de dégradations complexes et non entièrement maitrisées qui varient en fonction des conditions de fonctionnement. Cependant, il est admis qu’il est souhaitable de faire fonctionner la PEMFC à distributions de courant uniformes car des distributions de courant hétérogènes entraînent une mauvaise utilisation des réactifs et des catalyseurs, une diminution des performances globales et une possible dégradation des matériaux constitutifs du coeur de la pile. De nouvelles stratégies de diagnostic doivent donc être proposées en s’appuyant sur les distributions de courant. Mes travaux de recherche consistent à développer un nouvel outil de diagnostic s’appuyant sur une mesure du champ électromagnétique externe (non invasive) rayonné par la pile PEMFC. Le champ magnétique possède l’intérêt d’être corrélé à la distribution locale du courant circulant à l’intérieur de la pile, et permet d’avoir des informations sur les performances locales. Cette distribution est liée aux conditions opératoires de la pile. Il est alors possible, à partir d’une signature magnétique de remonter à une information locale et à la cause des distributions de courant non uniformes. Des bases (vecteurs) qui contiennent les données des champs magnétiques issues des 30 capteurs disposés autour de la PAC sont construites à partir de distributions de courant spécifiques. Ces bases constituent un espace de représentation du comportement anormal de la PEMFC et permettront de d’élaborer des signatures caractérisant les fonctionnements indésirables. Ainsi, deux méthodes ont été développées pour permettre : (i) d’extraire des paramètres pertinents sur la répartition de la densité de courant traduisant les performances locales de la PAC, (ii) de classifier les différents modes de fonctionnements indésirables. La première méthode consiste à générer des résidus vectoriels en comparant le comportement réel du système (caractérisé par un vecteur mesure) avec les bases générées. Des variables qualitatives ont été élaborées pour classifier les modes de fonctionnement indésirables de la pile. La deuxième méthode consiste à extraire des paramètres à partir de la projection du vecteur mesure dans la direction des bases. La classification est réalisée dans des espaces 2D. Une validation des deux méthodes proposées a été effectuée à partir de mesures expérimentales sur une PEMFC de taille industrielle (stack GENEPAC de 40 cellules construit par le CEA et PSA). La pertinence des paramètres extraits a été vérifiée en s’appuyant sur des distributions de courant mesurées directement. Les modes de fonctionnement indésirables prédéfinis permettent de localiser les paramètres opératoires ayant conduit à l’évolution de la distribution de courant. Les outils ainsi réalisés sont très facilement transposables à d’autres piles PEMFC. / Proton exchange membrane fuel cell (PEMFC) is a potential alternative energy conversion device for stationary and automotive applications. Wide commercialization of PEMFC depends on progress that can be achieved to enhance its reliability and durability. The PEM fuel cell is subject to several types of complex and not fully mastered degradations which vary with operating conditions. It is desirable to operate the PEMFC at uniform current distribution because non uniform current distribution over the MEA could result in poor reactant and catalyst utilization, overall cell performance degradation as well as corrosion processes inside the PEM fuel cell. Therefore, new diagnostic strategies must be proposed, including choice of information gathered on the system and the fuel cell operation representation. My research is to develop a new diagnostic tool based on a measure of the external electromagnetic field (non-invasive) radiated by the fuel cell. The magnetic field has the advantage of being correlated to the local distribution of the current flowing inside the fuel cell (a physical indicator to obtain information on local performance of a fuel cell); it is linked to the local operating conditions: relative humidity level, temperature etc. It is then possible, from a magnetic signature to trace local information. Baselines (vectors) which contain the magnetic fields data generated by specific current distribution are built to characterize the magnetic field generated by the undesirable operation of the fuel cell. Baselines constitute a representation space of abnormal system behavior. Two methods have been developed to enable: (i) to extract the relevant parameters on the distribution of the current density resulting from PEM fuel cell stack local performance, (ii) to classify different types of undesirables operations. The first method is to generate vector residuals by comparing the actual behavior of the system (characterized by a measurement vector) with the baselines generated. Qualitative variables were created to classify the undesirable modes of PEM fuel cell stack operation. The second method is to extract parameters from the projection of the vector in the direction of measurement baselines. The classification is performed in 2D space. Validation from experimental measurements of the two proposed methods has been carried out on a commercial scale PEMFC (GENEPAC stack of 40 cells built by the CEA and PSA). The relevance of the extracted parameters was verified based on current density distributions measured directly. The undesirable predefined operating modes were used to locate the operating conditions parameters that led to the evolution of the current density distribution. The tools are made easily transferable to other PEMFC stack.

Desenvolvemos um modelo na forma de um mapeamento bidimensional simplético (conservativo) para estudar a evolução das linhas de campo magnético de um plasma confinado no interior de um tokamak. Na primeira parte, consideramos dois perfis estudados na literatura para a densidade de corrente no plasma: um monotônico e um não-monotônico, que dão origem a diferentes perfis analíticos do fator de segurança. Nas simulações, consideramos inicialmente o sistema no equilíbrio, onde observamos, nas seções de Poincaré, apenas linhas invariantes. Em seguida, adicionamos uma perturbação (corrente externa), onde observamos cadeias de ilhas e caos no sistema. Na segunda parte consideramos um perfil também não-monotônico, mas com uma região na qual a densidade de corrente no plasma torna-se negativa, estudo ainda em aberto na literatura, que causa uma divergência no perfil do fator de segurança. Mesmo considerando o sistema apenas no equilíbrio, surgiram cadeias de ilhas muito pequenas em torno de curvas sem shear e caos localizado no sistema, característica não verificada para os outros perfis estudados no equilíbrio. Variando parâmetros relacionados à expressão da densidade de corrente, conseguimos controlar o aparecimento de regiões com cadeias de ilhas em torno de curvas sem shear e regiões caóticas. Para comprovar os resultados, aplicamos o perfil considerado a um outro mapa simplético da literatura (tokamap). Na parte final, consideramos a configuração do perfil do fator de segurança na forma de um divertor. Nessa configuração também temos uma divergência na expressão do perfil do fator de segurança. Observamos características similares (cadeias de ilhas em torno de curvas sem shear e caos) quando consideramos o perfil não-monotônico com densidade de corrente reversa. / We develop a symplectic (conservative) bidimensional map to study the evolution of magnetic field lines of a confined plasma in a tokamak. First, we considered two profiles for the plasma current density, studied in the literature: monotonic and non-monotonic, which give rise to different profiles for the poloidal magnetic field and different analytical profiles for the safety factor. In our simulations, we consider the system initially at equilibrium, where we observe, in Poincaré sections, only invariant lines. Then, we add a perturbation (external current), where we observe island chains and chaos in the system. In the second part, we consider a non-monotonic profile, but with a region which the current density becomes negative, which causes a divergence in the safety factor profile. Even considering only the sistem at equilibrium, very small island chains appeared around the shearless curves, and localized chaos. This feature was not observed for the other profiles at equilibrium. We can control the appearance of the regions with island chaind around the shearless curves and chaotic regions, by variation of parameters related to the density current expression. To comprove our results, we aplly the same profile to the other symplectic map. Finally, we consider a safety factor profile in a divertor configuration. We also have a divergence on in the safety factor profile. We observe similar features (island chains around shearless curves and localized chaos) when we consider a non-monotonic safety factor profile with a reversed density current.

Philosophiae Doctor - PhD / Ammonia has attracted attention as a possible fuel for direct fuel cells since it is easy to handle under low pressure, costs only slightly higher than methanol and can easily be cracked down into hydrogen and nitrogen. At low temperature, ammonia oxidation on noble metal electrodes is a sluggish reaction and efficient catalysts are required to convert ammonia to nitrogen and hydrogen at reasonable reaction rates. In this thesis, I present polycrystalline and oriented nanoalloys synthesised at room temperature in aqueous media and their catalytic effects on the oxidation of ammonia. The electro-oxidation of ammonia on palladium-goldsilver (PdAuAgNPs) ternary nanoalloys was systematically studied in alkaline solution of potassium hydroxide (KOH) by cyclic voltammetry (CV). The PdAuAg nanoalloys were prepared through a facile synthesis with ascorbic acid as a reductant and polyvinylpyrrolidone (PVP) as a stabilising agent from aqueous solutions of PdCh/HAuCI4.3H20/AgN03 mixtures. UV-visible spectroscopy was used to confirm the complete reduction of the metal ions; absorption peaks observed at 260 nm, 285 nm and 420 nm for Ag", Au3+ and Pd2+ ions respectively, disappeared after reduction indicating a complete reduction of the metal ions to zero-valent nanoparticles. High resolution transmission electron microscopy (HR TEM) revealed the formation of crystalline nonaggregated 25-35 nm sized nanoalloys. The elemental composition of the nanoalloys measured using energy dispersive X-ray spectroscopy (EDX) showed the presence of the three elements; Pd, Au and Ag. The well-dispersed non-agglomerated PdAuAg nanoalloys exhibited a reduced overpotential and a 33%, 400%,82% and 54% increase in current density for ammonia electro-oxidation compared to Pd, PdAg, PdAu nanoparticles and bare Pt electrode, respectively. The much improved current density of the well-dispersed PdAuAg nanoalloys is attributed to the increased electrochemically active surface area of the nanoalloys. This electro catalytic behaviour of the PdAuAg nanoalloys for ammonia oxidation in KOH solutions provides a promising route for development of low-cost and high performance electro catalyst for electro-oxidation of ammoniaMoreover, ammonia oxidation on platinum surfaces has been found to be a very structure sensitive reaction which takes place almost exclusively on Pt(100) surfaces. I report for the first time the preparation of sodium polyacrylate-capped Pt(100)Pd, pte 1OO)Au, pte 1OO)Ir, Pt(IOO)Rh, Pt(100)PdAu, Pt(100)IrAu, Pt(IOO)PdIr and Pt(IOO)RhAu nanoalloys. The reduction of the metal ions to nanoparticles was confirmed by UV-visible spectroscopy while the shapes and the structures of the nanoparticles were studied using HRTEM and CV. HRTEM analysis showed well distributed non-agglomerated 5-20 nm semi-spherical and cubic nanoalloys with lattice fridges on their surfaces indicating the crystalline nature of the nanoalloys. Pt(100) nanoalloy systems showed particles with triangular and cubic shapes. The existence of the preferentially cubic shaped nanoparticles in the samples indicated that the nanoalloys had some (100) sites orientation/a significant amount of (100) sites at their surfaces. The CV of the nanoparticles in the hydrogen adsorption/desorption region (-200 mV to 100 mV vs. Ag! AgCl) was used to obtain qualitative information about the surface structure of the nanoparticles. The voltammogram of oriented Pt(100) nanoparticles showed very clearly the presence of adsorption states associated with (110) sites, (100) domains and (l00) sites at -131 mV, -34 mV and 29 mV, respectively. The companson of this voltammetric profile with that obtained for a Pt(100) single crystal electrode clearly points out that the synthesised Pt nanoparticles have a high density of (100) sites. However, the peak that was observed at 29 mV in the CV of Pt(100) nanoparticles was not present in the vo ltammo grams of the Pt(100) nanoalloy systems confirming the formation of the nanoalloys. The results reported in this work demonstrate the importance of controlling the intrinsic structural properties of Pt nanoparticles; in terms of nature of the active sites and the effect of adding adatoms (such as Au, Pd, Rh, Ir) in order to understand their catalytic properties. The electrochemical activities of these nanoparticles for ammonia oxidation in basic medium showed an increase of over 100% current density compared to Pt electrode. Pt(lOO)RhAu nanoalloys showed the highest catalytic properties while Pt(lOO)PdAu had the lowest as shown in the trend: Pt(lOO)RhAu > Pt(lOO)PdIr > Pt(lOO) > Pt(lOO)IrAu > Pt(lOO)Pd> Pt(lOO)Rh > Pt(lOO)Au > Pt(lOO)Ir > Pt(lOO)PdAu. The synthesised oriented nanoalloys were further interrogated towards the oxidation of hydrazine as a fuel for hydrazine fuel cells. The oriented Pt(lOO) nanoparticles and Pt(lOO) nanoalloy systems exhibited over 1000% increase in current density and reduced oxidation overpotential compared to bare glassy carbon electrode. These excellent catalytic properties are attributed to the increased surface area and the presence of (100) sites which favour the oxidation of hydrazine.

The aim of the project was to prepare the given model of the current path in the environment of the SolidWorks programme, in order to simulate the flow path in the environment of the Ansys programme, where there was calculated the distribution of current density,voltage drops and heat loss on the the specified current track according to specified conditions. The obtained results are analyzed at the conclusion of this work.

The objective of this master´s thesis is diagnostic the actual disconnector current path that is unevenly stressed by nominal current. The most stressed parts are excessively heated. In next part are projected a few options to optimize the current path. The options are verified by simulation. The best option is recommended to the submitter.