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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
111

Constru??o e valida??o de um receptor GPS para uso espacial

Albuquerque, Glauberto Leilson Alves de 20 November 2009 (has links)
Made available in DSpace on 2014-12-17T14:55:41Z (GMT). No. of bitstreams: 1 GlaubertoLAA.pdf: 3487440 bytes, checksum: bcd5cef1c854f4d01f9c73419e1d7d42 (MD5) Previous issue date: 2009-11-20 / Global Positioning System, or simply GPS, it is a radionavigation system developed by United States for military applications, but it becames very useful for civilian using. In the last decades Brazil has developed sounding rockets and today many projects to build micro and nanosatellites has appeared. This kind of vehicles named spacecrafts or high dynamic vehicles, can use GPS for its autonome location and trajectories controls. Despite of a huge number of GPS receivers available for civilian applications, they cannot used in high dynamic vehicles due environmental issues (vibrations, temperatures, etc.) or imposed dynamic working limits. Only a few nations have the technology to build GPS receivers for spacecrafts or high dynamic vehicles is available and they imposes rules who difficult the access to this receivers. This project intends to build a GPS receiver, to install them in a payload of a sounding rocket and data collecting to verify its correct operation when at the flight conditions. The inner software to this receiver was available in source code and it was tested in a software development platform named GPS Architect. Many organizations cooperated to support this project: AEB, UFRN, IAE, INPE e CLBI. After many phases: defining working conditions, choice and searching electronic, the making of the printed boards, assembling and assembling tests; the receiver was installed in a VS30 sounding rocket launched at Centro de Lan?amento da Barreira do Inferno in Natal/RN. Despite of the fact the locations data from the receiver were collected only the first 70 seconds of flight, this data confirms the correct operation of the receiver by the comparison between its positioning data and the the trajectory data from CLBI s tracking radar named ADOUR / O Sistema de Posicionamento Global, conhecido mundialmente pala sigla GPS, ? um sistema de radionavega??o constru?do pelos norte-americanos com inten??es militares, mas que encontraram, com o passar do tempo, muitas aplica??es de uso civil. No Brasil, al?m do desenvolvimento de foguetes de sondagem, come?am a aparecer projetos de constru??o de micro e nanosat?lites. Estes ve?culos denominados espaciais ou de alta din?mica podem, quando em voo, usufruir do sistema GPS para localiza??o aut?noma e verifica??o/controle das suas trajet?rias. Apesar da enorme disponibilidade de receptores GPS no mercado civil, estes n?o podem ser utilizados em ve?culos de alta din?mica, seja por quest?es ambientais (vibra??es, temperaturas elevadas, etc.) ou por prote??o l?gica (via software). Os receptores para uso em ve?culos de alta din?mica, ou ve?culos espaciais, fazem parte de uma tecnologia restrita a poucos pa?ses, que estabelecem regras muito r?gidas para suas aquisi??es. O presente projeto objetiva construir e validar funcionamento b?sico deste receptor ao instal?-lo num foguete de sondagem e coleta de dados em voo. O software a ser utilizado no receptor j? estava dispon?vel em c?digo fonte e testado em uma plataforma de desenvolvimento denominada GPS Architect. V?rios organismos cooperaram para realiza??o projeto: AEB, UFRN, IAE, INPE e CLBI. Ap?s v?rios passos para realiza??o do projeto: defini??o das condi??es de funcionamento, escolha e aquisi??o dos componentes eletr?nicos, fabrica??o das placas de circuito impresso, montagem e testes de integra??o; o mesmo foi instalado num foguete de sondagem VS30 lan?ado a partir do Centro de Lan?amento da Barreira do Inferno em Natal/RN. Apesar da coleta parcial dos dados do receptor, por falha t?cnica do sistema de telemetria do foguete, os resultados obtidos foram suficientes para validar o funcionamento do receptor a partir da compara??o entre os dados de trajetografia fornecidos pelo receptor GPS e o radar de trajetografia do CLBI conhecido como Radar ADOUR
112

Ve?culos a?reos n?o tripulados e sistema de entrega: estudo, desenvolvimento e testes / Unmanned aerial vehicles and delivery system: study, development and testing

Medeiros Neto, Manoel Pedro de 29 February 2016 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-12-15T16:27:02Z No. of bitstreams: 1 ManoelPedroDeMedeirosNeto_DISSERT.pdf: 3664081 bytes, checksum: f1856f73174bde3b90b40604d7d1ae0e (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-12-15T16:36:27Z (GMT) No. of bitstreams: 1 ManoelPedroDeMedeirosNeto_DISSERT.pdf: 3664081 bytes, checksum: f1856f73174bde3b90b40604d7d1ae0e (MD5) / Made available in DSpace on 2016-12-15T16:36:27Z (GMT). No. of bitstreams: 1 ManoelPedroDeMedeirosNeto_DISSERT.pdf: 3664081 bytes, checksum: f1856f73174bde3b90b40604d7d1ae0e (MD5) Previous issue date: 2016-02-29 / Ve?culos n?o tripulados est?o cada vez mais presentes no cotidiano das empresas e das pessoas, pois esse tipo de ve?culo est? de forma crescente desempenhando atividades que anteriormente eram apenas executadas por seres humanos. No entanto, para se compreender melhor o potencial de ve?culos n?o tripulados, ? importante conhecer seus tipos, caracter?sticas, aplica??es, limita??es e desafios, pois somente com esse conhecimento pode-se entender as potencialidades do uso de ve?culos dessa natureza em aplica??es variadas. Nesse contexto, na primeira parte desta pesquisa foram estudados os diferentes tipos de ve?culos n?o tripulados, i.e. terrestres, aqu?ticos, a?reos e h?bridos. Durante a segunda fase da pesquisa, foi realizado um aprofundamento tendo como foco as interfaces de usu?rio para controle dos ve?culos a?reos n?o tripulados. Esses dois levantamentos iniciais do dom?nio, permitiram a identifica??o de desafios e oportunidades para o desenvolvimento de novas aplica??es para esse contexto. Com base no conhecimento adquirido com esses estudos, ent?o, foi desenvolvido um sistema de entrega automatizada de objetos para o campus de Universidades, denominado de PostDrone University, e desenvolvido um ve?culo a?reo n?o tripulado para realizar as entregas, denominado de PostDrone University UAV K-263. O sistema possui uma interface de usu?rio de f?cil uso, que n?o requer conhecimentos de dom?nios espec?ficos como avia??o ou controle de aeronaves para sua opera??o. Por fim, diversos testes foram realizados com o intuito de validar e identificar as limita??es da solu??o desenvolvida nesta pesquisa. / Unmanned vehicles are increasingly present in the daily of companies and people, because this kind of vehicle is performing ever more tasks that were previously only executed by human beings. However, to better understand the potential of unmanned vehicles, it is important to know their types, features, applications, limitations and challenges, thus with this knowledge it is possible to comprehend the possibilities of use of these vehicles in several applications. In this context, the first step of the present research consists in studying the different kinds of unmanned vehicles, i.e., ground, surface and underwater, aerial, and hybrid. During the second step of the research, a deepening study was accomplished, with focus on user interfaces of unmanned aerial vehicles. These two initial reviews of the domain allowed the identification of challenges and opportunities to the development of new applications for this context. Based on the acquired knowledge from these studies, then, an automated goods delivery system was developed for universities? campuses, called PostDrone University, and an unmanned vehicle to make the deliveries, called PostDrone University UAV K-263, was also developed. The system has an easy use UI, which does not require the user to have knowledge about specific domains, as aviation or aircraft control, for the operation of the system. Lastly, several test were accomplished aiming to validate the solution proposed in the present research and identify its limitations / 2018-03-31
113

Zdravotní systém Německa / The health system of Germany

Koubová, Lenka January 2017 (has links)
The diploma thesis contains a comprehensive view of the health system in the Federal Republic of Germany in 1995-2015. The main aim of this work is to establish recommendations for improvement of the Czech health system based on the evaluation of the findings on the German health system. The partial aims of the diploma thesis are the characteristics of the health system and the analysis of income and expenditure in health care in Germany. The thesis is divided into six chapters. The first chapter is focused on the information obtained from professional literature. In particular, it describes the different concepts related to healthcare and its financing. The second chapter focuses on the economic concept and the issue of the health system. The third part contains a description of the country's health system. Here are also some selected data about Germany, organization or authority at federal, state and local levels. The fourth chapter deals with the insurance market in Germany. The fifth part summarizes the fundamental reforms of the health system of the Federal Republic. The last chapter is an analysis of income and expenditure of the health system. This section analyzes the data available from statistics from the German Statistical Office or from multinational organizations such as WHO, OECD or the World Bank.
114

Středoškolská výuka geografie obyvatelstva a sídel s využitím tabletů / Teaching population and settlement geography at high schools with tablets

Měkota, Tomáš January 2017 (has links)
Using of modern technologies has been increasing in the sectors of economic and by people. If educational system shall prepare students for the future, it should learn them to work with that technologies, for example computers or tablets. Modern technologies have been entering to schools increasingly but very slowly. Effects of their usage in the educational process have not been examined sufficiently. This thesis applies to advantages and disadvantages of teaching population and settlement geography with a tablet, particularly using the Nearpod application. The influence of teaching with tablet on students' test results is analyzed on the basis of taught lessons and didactic tests. Then, advantages and disadvantages of tablet using at school are established for students and teachers according to interviews and observation during the lessons. This study shows that tablet using does not have to mean higher students' scores in the tests. Students are more motivated, lessons are more entertaining for them in comparison to traditional lessons. Tablets also provide priceless feedback to them. From the teacher's perspective, lessons with tablets are more time-consuming than traditional lessons, but they provide possibilities to observe all students' work during the lesson and more possibilities to...
115

La signalisation wnt/frizzled dans la vasculogenèse et l’angiogenèse : frizzled-7, un nouvel acteur de la formation des vaisseaux / Wnt/frizzled pathway in vasculogenesis and angiogenesis : frizzled-7, a new actor of vessel formation

Ferreira Tojais, Nancy 19 October 2010 (has links)
L’obstruction des vaisseaux est responsable d’ischémie tissulaire dans différents territoires périphériques, cardiaques et cérébraux. Un des mécanismes d’adaptation du tissu à l’ischémie est la formation de néo-vaisseaux. Plusieurs données récentes mettent en évidence un rôle de la voie de signalisation Wnt/Frizzled (Fzd) dans le développement vasculaire. Le travail de cette thèse s’est focalisé sur l’étude du récepteur Frizzled7 (Fzd7) et de son rôle dans la formation des vaisseaux. Le modèle des corps embryoïdes, un modèle de différenciation des cellules souches embryonnaires vers le phénotype endothélial, nous a permis de démontrer que Fzd7 était exprimé au cours des différentes étapes de différenciation endothéliale. Des études sur des cellules endothéliales matures nous ont permis de montrer que Fzd7 régulait différentes propriétés des cellules endothéliales dont la migration et la formation de tubes endothéliaux, mais pas la prolifération. De plus, Fzd7 participe à la stabilité des jonctions cellulaires en interagissant avec la VE-cadhérine. Concernant les mécanismes moléculaires mis en jeu par Fzd7, nous avons pu montrer que celui-ci était capable d’activer la voie Wnt/PCP via la phosphorylation de la protéine JNK. Enfin, une étude in vivo dans le modèle du poisson Zèbre, nous a permis de mettre en évidence un rôle de Fzd7 dans la formation des vaisseaux intersomitiques. La deuxième partie de ce travail concerne le rôle de la voie Wnt/Fzd dans les propriétés angiogèniques des cellules souches mésenchymateuses (CSM). L’objectif de cette étude était de définir comment les CSM participaient à la formation des vaisseaux et si le système Wnt/Frizzled était nécessaire. Nous avons pu montrer que sFRP1, un modulateur de la voie Wnt, améliore la fonction cellulaire des CSM et contribue à la maturation des néo-vaisseaux. De plus, nous avons pu montrer que les CSM implantées dans un modèle d’ischémie du membre inférieur amélioraient la réponse angiogénique lorsque celles-ci étaient préconditionnées en hypoxie. Nous avons mis en évidence le rôle de Wnt4 dans ce processus. / The obstruction of the vessels is responsible for ischemia in various outlying areas, heart and brain. One of the mechanisms of tissue adaptation to ischemia is the formation of neo-vessels. Several recent data show a role of Wnt/Frizzled (Fzd) pathway in vascular development.The work of this thesis focused on the study of receptor Frizzled7 (Fzd7) and its role in vessel formation. Using the model of embryoid bodies, a model of embryonic stem cell differentiation toward the endothelial lineage, we demonstrated that Fzd7 was expressed during different stages of endothelial cell differentiation. Studies on mature endothelial cells have shown that Fzd7 regulates endothelial cells properties including migration and endothelial tube formation but not proliferation. In addition, Fzd7 participates in the stability of cell junctions by interacting with VE-cadherin. Regarding the molecular mechanisms involved in Fzd7 signalling, we could show that this receptor was capable of activating the Wnt/PCP pathway via phosphorylation of JNK protein. Finally, an in vivo study in zebrafish model, allowed us to highlight a role of Fzd7 in intersomitic vessel formation.The second part of this work concerns the role of the Wnt/Fzd pathway in the angiogenic properties of mesenchymal stem cells (MSC). The objective of this study was to determine how CSM participated in vessel formation and if the Wnt/Frizzled pathway was necessary. We show that sFRP1, a modulator of the Wnt pathway, improves cellular function of MSCs and contributes to the maturation of neo-vessels. In addition, we have shown that MSCs implanted in a model of lower limb ischemia improved the angiogenic response when they were preconditioned by hypoxia. We have highlighted the role of Wnt4 in this process.
116

Bezdětnost a sítě sociální podpory ve stáří / Childlessness and social support net in old age

Křenková, Lenka January 2017 (has links)
The main goal of this study is to discover whether there is a significant difference between childless individuals and parents based on their social contact and support received in old age. Firstly, the theoretical background is introduced. The demographical development of childlessness in the Czech Republic is then analyzed while also mentioning the limitations of the data sources that we face. Childlessness is then put into the context of possible social isolation, a lack of support in the household or in receiving personal care in old age. It was proven that with increasing age the frequency of social contact with friends decreases, however, this does not apply to contact with family members. Using data from SHARE research we have proved that the childless elderly are more intensively socially active than parents. However, in financial transfers parents give more and especially to their children, whereas the childless invest in a broader range of family and nonfamily circles. There was no significant difference in receiving personal care or practical help in the household between parents and the childless, although differences were shown based on age, health, gender, education and the marital status of respondents. The most common people who provide personal care or practical help in the household (even...
117

Sociální pracovník v organizační struktuře zdravotnického zařízení / Social worker within the organizational structure of a medical facility

Svoboda, Marian January 2021 (has links)
The diploma thesis focuses on the work of social and health-social workers in a selected medical facility. The paper is designed as a theoretical introduction to the issue of social work in health care, especially focused on the position of the social or health-social worker at a healthcare facility. Furthermore, there are described competencies of social workers, and the specifics of cooperation in multidisciplinary teams of medical facilities. The theoretical part also consists of chapters focused on human motivation and stress, which social workers may experience during the performance of their work. The empiric part of this diploma thesis presents the research, which aim is to describe the position of social workers in the selected medical facility, characterize the limits in the work of social workers resulting from this position and define their satisfaction with their current position within the organizational structure of the selected medical facility. The research was carried out using the method of a semi-structured interview. The informants of the research were social and health-social workers from a specific medical facility. Among other things, the work answers the question of whether social workers feel themselves to be a part of multidisciplinary teams or still see reserves at...
118

In situ Untersuchungen der mechanochemischen Synthese von Cokristallen: Einfluss von Reaktionsparametern am Modellsystem Pyrazinamid

Kulla, Hannes 25 July 2019 (has links)
Die Mechanochemie findet zunehmend Verwendung für die Synthese neuer Verbindungen. Dennoch sind die beim Mahlen stattfindenden Prozesse weitestgehend unverstanden. Dahingehend wurde in dieser Arbeit eine Dreifachkopplung aus in situ Synchrotron-Röntgenbeugung, Raman-Spektroskopie und Thermographie entwickelt, um mechanochemische Reaktionen unter realistischen Bedingungen in Echtzeit zu verfolgen. Dadurch konnten tiefgreifende Einblicke in den Reaktionsverlauf und Temperaturverlauf beim Mahlen erhalten und neue metastabile Verbindungen isoliert werden. Für die Bildung pharmazeutischer Cokristalle diente Pyrazinamid als Modellsystem. Es konnten neue binäre und ternäre Verbindungen synthetisiert, detailliert charakterisiert und deren Kristallstruktur aufgeklärt werden. Die Abhängigkeit der Stabilität polymorpher Cokristalle von der Temperatur und den Synthesebedingungen konnte gezeigt werden. In Konkurrenzreaktionen konnten Trends hinsichtlich der bevorzugten Bildung eine bestimmten Cokristalls beobachtet werden. Mittels in situ Untersuchungen wurde der Einfluss zentraler Reaktionsparameter, wie die Mahlfrequenz, der Kugeldurchmesser, der eingesetzte Ausgangsstoff und die Zugabe von Lösungsmittel, auf die Induktions- und Reaktionszeit der Reaktion ermittelt. Basierend auf den gewonnenen Erkenntnissen konnte ein Diffusionsmechanismus für die mechanochemische Cokristallbildung abgeleitet werden. / Mechanochemistry is increasingly applied for the synthesis of new compounds. Still, the processes taking place during milling are far from being understood. In this thesis, a triple coupling of in situ synchrotron X-ray diffraction, Raman spectroscopy and thermography has been developed to follow mechanochemical reactions under realistic conditions in real time. This allowed deep insights into the reaction and temperature progression during milling and the isolation of new metastable compounds. For the formation of pharmaceutical cocrystals pyrazinamide served as a model system. New binary and ternary compounds were synthesized, characterized in detail and their crystal structure solved. The dependence of the stability of polymorphic cocrystals on temperature and synthesis conditions could be shown. In competitive reactions, trends regarding the preferred formation of a certain cocrystal have been observed. The influence of important reaction parameters, such as the milling frequency, the ball diameter, the starting material used and the addition of solvent, on the induction and reaction time of the reaction was determined by means of in situ investigations. Based on the gained knowledge, a diffusion mechanism for the mechanochemical cocrystal formation could be derived.
119

Investigations of Electron Transfer at Graphene and Graphene Sandwiches / Role of Interfacial Charges and Influence of Subsurface Metal

Wehrhold, Michel 31 January 2022 (has links)
Mit der Entdeckung von Graphen begann ein neuer Zeitabschnitt für die Entwicklung von Elektronik und Sensoren aufgrund der einzigartigen elektronischen Struktur Graphens. Graphen ist breit vertreten, beispielsweise in Anwendungsbereichen von Sensorik, Energiespeicherung und Katalyse. Elektronentransferprozesse sind fundamentale Prozesse für eben solche Anwendungen. Die Eigenschaften des heterogenen Elektronentransfers von Graphen sind sehr umstritten und es gibt immer noch kein einheitliches Bild, um eben jenen zu verstehen, da oft voneinander abweichende Eigenschaften in der Literatur dargestellt werden. Diese Arbeit präsentiert systematische Untersuchungen der Elektronentransfereigenschaften von einlagigen Graphenelektroden. Als weiterer Teil dieser Arbeit werden die Elektronentransfereigenschaften durch den Entwurf einer neuen Graphen-Hybridelektrode gezielt verändert. Der erste Teil ist auf die Verbesserung der Herstellungsschritte und der anschließenden Untersuchung des Einflusses von Kupferrückständen auf die Kinetik des Elektronentransfers von einlagigen Graphenelektroden fokussiert. Die Kupferrückstände kommen von der Herstellung und dem Transfer von Graphen. Die Elektronentransferkinetik von klassischen Redoxmediatoren mit inner-sphere Elektronentransfermechanismus nimmt nach erfolgreichen Entfernen von Kupferrückständen ab. Im Gegensatz dazu bleibt die Kinetik von outer-sphere Redoxmediatoren unberührt. Hier wird gezeigt, dass die Elektronentransferkinetik von solchen Redoxmediatoren vom pH-Wert der Lösung abhängig ist, obwohl bei dem Elektronentransfer Protonen nicht involviert sind. Weiterhin wird hier festgestellt, dass der Elektronentransfer von Kationen an Graphen am schnellsten in neutralem pH stattfindet, während der Elektronentransfer von Anionen am schnellsten in saurem Millieu abläuft. Diese pH-Abhängigkeit wird den elektrostatischen Wechselwirkungen zwischen den dissoziierten Redoxmediatoren und der Ladung der Graphen-Flüssigkeit-Grenzschicht zugeschrieben. Dieses Verhalten wird auch für Graphenelektroden auf anderen isolierenden Substraten und sogar mit einer unter dem Graphen liegenden Schicht von hexagonalem Bornitrid (hBN) gefunden. Basierend darauf ist die Schlussfolgerung, dass diese pH-Abhängigkeit für den Elektronentransfer von geladenen Redoxmediatoren an Graphenelektroden intrinsisch und spezifisch für Graphen ist. Mit Metallsubstraten unter dem Graphen kann dieser pH-Effekt unterdrückt werden, was für einen verstärkten elektrokatalytischen Effekt vom darunterliegenden Metall spricht, welcher dem vorher diskutierten elektrostatischen Effekt, vermutlich durch die Zunahme der gesamten Elektronendichte, überwiegt. Basierend darauf wurde eine neue Art von Graphenelektrode entwickelt: die Graphen-Sandwichelektrode. Diese Elektrode besteht aus zwei aufeinanderliegenden Graphenschichten mit dazwischenliegenden Metallpartikeln. Diese Sandwichelektrode nutzt die elektrochemischen Eigenschaften der in der Mitte liegenden Metallpartikeln aus, obwohl das Metall durch eine Graphenschicht bedeckt ist und nicht in Kontakt mit der Lösung kommt. Bei der Verwendung von Platinpartikeln wird die obere Graphenschicht mit elektrokatalytischen Eigenschaften versehen. Als Ergebnis wird die Bildung von Wasserstoff (HER) und die Reduktion von Sauerstoff (ORR) an dieser Elektrode katalysiert. Des Weiteren wird dieser Effekt hier dafür genutzt um Wasserstoffperoxid zu messen, auch wenn eine solche Reaktion an einer „normalen“ Graphenelektrode nicht beobachtet werden kann. Hierdurch wird eine neue Klasse von optimierten Elektroden mit maßgeschneiderten elektrokatalytischen Eigenschaften realisiert. Diese Ergebnisse heben den Einfluss eines unter Graphen liegenden Metalls auf die Elektrochemie von Graphen hervor. Der zweite Teil dieser Arbeit konzentriert sich auf die Untersuchungen von Ladungen an der Graphen-Flüssigkeit-Grenzschicht auf einem lokalen und räumlich aufgelösten Niveau mit Hilfe von Rasterionenleitfähigkeitsmikroskopie (Scanning Ion Conductance Microscope - SICM). Dafür sind weiche Trägerflächen benötigt, die die Spitzen von Glaskapillaren nicht beschädigen. Diesbezüglich werden drei Protokolle für den Transfer von Graphen auf ein weiches Polymersubstrat, dem Polydimetyhlsiloxan (PDMS), entwickelt. Die dadurch erhaltenen Graphenproben werden mit Hilfe von optischer und Rasterkraftmikroskopie charakterisiert. Anhand von Annäherungskurven aus der SICM kann die Oberflächenladung qualitativ charakterisiert werden. Die Oberflächenladung einer Graphenoberfläche kann als negativ geladen in einem pH-Wert von 7 entschlüsselt werden. Zusätzlich werden Herausforderungen und Hindernisse beim Arbeiten mit SICM zu Grenzflächenuntersuchungen von einlagigem Graphen diskutiert. Diese Ausarbeitung zeigt die Bedeutung von Grenzflächenladungen und den Einfluss von unter dem Graphen liegenden Metall auf Graphen und graphenverwandte Elektroden auf. Dieses Wissen kann genutzt werden, um neue graphenbasierte Sensoren und auch hybride Elektroden für Elektrokatalyse zu entwickeln. / The discovery of graphene initiated a new era of electronic and sensor development due to graphene's unique electronic structure. Graphene covers a wide range of applications including sensing, energy storage and catalysis. The heterogeneous electron transfer (ET) is the most fundamental and most important process happening at devices in such applications. However, the ET properties of graphene are highly debated and still no coherent picture can be drawn to understand them since differing ET rates are presented in literature. This work presents systematic investigations of the ET characteristics of graphene monolayer electrodes. Furthermore, the ET properties are engineered by the fabrication of a novel graphene-based hybrid electrode. The first part focusses on the improvement of the fabrication steps and subsequent investigation of the influence of Cu trace residues on the ET kinetics of graphene monolayer electrodes. The residual Cu traces come from the fabrication process of graphene as well as from the transfer process of graphene monolayer electrodes. The ET kinetics of a classical inner-sphere redox probe decreases after a successful removal of Cu particles. In contrast to this, the ET kinetics for outer-sphere redox probes stay unaffected. Most importantly, the ET kinetics of both kinds of redox probes are found to be dependent on the solution pH, although these reactions are proton independent. ET at graphene with cations is found to be fastest in neutral pH, while the ET kinetics of anions are fastest in acidic media. This pH dependency is attributed to electrostatic interactions between the dissociated redox probes and the interfacial charge at the graphene-liquid interface (GLI). This behavior is further observed for graphene monolayer electrodes on other insulating substrates. Even with an underlying hexagonal boron nitride (hBN) layer that shields the graphene monolayer from the substrate, the same pH effect can be observed. Based on this, it can be concluded that the pH dependency of ET at graphene for charged redox species is intrinsic to graphene. By using a subsurface metal substrate, the pH effect is suppressed, indicating an enhanced electrocatalytic effect from the metal underneath that dominates the afore discovered electrostatic effect, most likely due to an increase of the overall electron density. By exploiting this effect, a new kind of graphene electrode is designed: the graphene sandwich electrode. This electrode consists of two graphene monolayers, with electrodeposited metal particles between both layers. This sandwich electrode exploits electrochemical properties of the metal in between, even though the metal is covered by a graphene monolayer and hence not exposed to the liquid. By using Pt particles, the upper graphene layer gets rendered with electrocatalytic properties. As a result, the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) are found to be clearly catalyzed at this electrode. Furthermore, this effect is exploited for hydrogen peroxide sensing, while this reaction is not observable on pristine graphene. Thus, a new kind of engineered electrode with rendered novel electrocatalytic properties was designed. These findings highlight the influence of a subsurface metal on to the electrochemistry of graphene. The second part of this work focusses on using scanning ion conductance microscopy (SICM) to investigate interfacial charges at the GLI at a local and spatially resolved level. First, for investigations using an SICM, soft samples are needed for avoiding damage of SICM tips. For this, three different protocols are developed and discussed for transferring a graphene monolayer on a soft poly(dimethylsiloxane) (PDMS) substrate. The obtained graphene samples are characterized using optical and atomic force microscopy. By utilizing approach curves in SICM, the surface charge can be characterized qualitatively. At a graphene surface in pH 7, an overall negative surface charge can be deciphered. In addition, challenges and obstacles are discussed when using SICM for interfacial investigations of graphene monolayers. Taken together, this work presents systematic investigations of the ET of graphene monolayer and graphene sandwich electrodes. These findings improve the understanding of graphene electrochemistry and highlights the importance of interfacial charge and the influence of a subsurface metal on graphene and graphene-related electrodes. This knowledge can be used to design new graphene-based sensors and hybrid electrodes for electrocatalysis.
120

Modèles et protocoles pour les interactions des véhicules électriques mobiles avec la grille

Said, Dhaou January 2014 (has links)
Dans de proches années, les véhicules électriques (VEs) vont faire leur apparition massive sur les marchés. Cela peut avoir un impact important sur le fonctionnement des réseaux d’électricité actuels qui devront ajuster leur fonctionnement à la nouvelle demande massive d'électricité provenant des VEs. Par contre, les VEs peuvent aussi être vus comme une nouvelle opportunité dans le futur marché d’électricité. En effet, une décharge/recharge intelligente peut permettre aux VEs d’être un support de stockage d’électricité important, valable, et permanent dont la capacité croit en fonction du nombre des VEs. Ce projet a comme objectifs de : (1) proposer un schéma d’interaction V2G (Vehicle-to-Grid) intégrant des techniques permettant de : (a) adapter le fonctionnement de la grille aux contraintes temporelles et spatiales relatives au processus de recharge des VEs dans un milieu résidentiel. On cherchera à satisfaire de différentes demandes en puissance des VEs branchés au secteur sans trop stresser la grille intelligente, (b) optimiser les opérations de chargement/déchargement entre les VEs et la grille dans les deux sens. (2) Proposer de nouveaux schémas de communication sans fil, entre les VEs et la grille intelligente loin des bornes de recharge, qui soient basés sur les standards de communications véhiculaires (VANETs) ainsi que sur d’autres standards de communication à grande échelle. On introduira des techniques d’accès à la grille intelligente pour négocier le coût de recharge/décharge des batteries, le temps d’attente du service, les emplacements et aussi pour planifier la motivation du consommateur afin de favoriser la stabilité de la grille.

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