Made available in DSpace on 2014-06-11T19:32:51Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-06-26Bitstream added on 2014-06-13T19:43:38Z : No. of bitstreams: 1 zanfolim_aa_dr_bauru.pdf: 2078904 bytes, checksum: 89fecc6406c0fe251fffb9f3101d20dd (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram preparados filmes finos de ftalocianinas de zinco (ZnPc) e de níquel (NiPc) através da técnica de evaporação térmica à vácuo (PVD - physical vapor deposition) em diversas espessuras e em escala nanométrica com o objetivo de determinar a arquitetura molecular destes filmes bem como suas propriedades ópticas e elétricas. Em última análise buscam-se gerar subsídios para as possíveis aplicações, especialmente dispositivos eletrônicos a base de semicondutores orgânicos e sensores de gás. A ZnPc e a NiPc em pó foram caracterizadas utilizando-se as técnicas de termogravimetria (TG), calorimetria exploratória diferencial (DSC) e os filmes PVD por espectroscopias de absorção no ultravioleta-visível (UV-vis), no infravermelho com transformada de Fourier (FTIR), espalhamento Raman, difração de raios-X, microscopias óptica e de força atômica (AFM) e caracterização elétrica cc (tensão x corrente). Os resultados mostraram que é possível a fabricação de filmes PVD de ZnPc e NiPc, uma vez que estas moléculas não são termicamente degradadas durante o processo de evaporação térmica a vácuo, e que o crescimento dos filmes pode ser controlado em escala nanométrica para ambos os materiais. Em termos estruturais, os filmes PVD de ZnPc e NiPc são cristalinos (forma α) e possuem as moléculas arranjado-se na forma de agregados e monômetros e ordenadas com o anel macrociclo inclinado em relação à superfície do substrato. Tais agregados podem ser vistos em escala nanométrica, porém, em escala micrométrica os filmes apresentam-se morfologicamente homogêneos. Em relação às propriedades ópticas e elétricas, observou-se que ambos os filmes PVD absorvem na região do visível com a ZnPc apresentando fotoluminescência quando irradiado com laser 785 nm. A condutividade elétrica é de 1,2x'10 POT. -10' S/m para a ZnPc e de 72x'10 POT... / In this work thin films of phthalocyanines of zinc (ZnPc) and nickel (NiPc) were fabricated through the vacuum thermal evaporation technique (PVD - physical vapor deposition) for different thicknesses at nanometric scale with the objective of determining the molecular architecture of these films as well as their optical and electrical properties. The final idea is to generate subsidies for applications of these films in electronic devices based on organic semiconductors and gas sensors. The PVD films were characterized using thermogravimetry (TG), differential scanning calorimetry (DSC), ultraviolet-visible (UV-vis) and Fourier transform infrared (FTIR) absorption spectroscopies, Raman scattering, X-ray diffraction, optical and atomic force (AFM) microscopies, and electrical characterization (tension x current dc). The results showed that the fabrication of ZnPc and NiPc films is possible since these molecules are not thermally degraded during the process of vacuum thermal evaporation and that the growth of the films can be controlled at nanometric scale for both materials. Structurally, the PVD films of ZnPc and NiPc possess the molecules organized with the macrocycle ring tilted in relation to the substrate surface. They are crystalline (α form) and possess molecular aggregates in the form of dimmers or higher order of aggregates and monomers. Such aggregates can be seen at nanometric scale, however, at micrometric scale the films are morphologically homogeneous. In relation to the optical and electrical properties, it was observed that boh PVD films absorb in the visible region with the ZnPc presenting photoluminescence when irradiated with the 785 nm laser line. The electric conductivity at 1,2x'10 POT. -10' S/m for ZnPc and 72x'10 POT. -10' S/m for NiPc. They also presented photoconductivity with the ZnPc more photoconductor than NiPc. Finally, after thermal treatment... (Complete abstract click electronic access below)

The advent of experimental methodologies have led to decisive progress in the study of corrupt behaviour in the last two decades. Since they can complement survey data and perception indexes with controlled experimental data, scholars and policy makers have reached a better understanding of decision-making in bribery situations and are able to design innovative anticorruption policies.In this thesis, I use experimental and empirical data to contribute to the field of the economics of corruption. The first two chapters of this PhD dissertation use experimental methodologies to study decision-making in a bribery scenario. The first chapter tests an anti-corruption strategy with a lab in the field experiment in Burundi. The second chapter studies the fairness concerns that might arise when dealing with redistribution in a bribery situation. The third chapter uses an empirical analysis to explore the controversial issue of political moonlighting, i.e. having outside activities while holding public office. It investigates "double-hat politicians", who combine mayor and parliamentary positions in Wallonia.In a first chapter, written with Jean-Benoit Falisse, we explore the effect of anti- corruption messages on corrupt behavior and public service delivery. In a novel lab-in-the-field experiment, 527 public servants from Burundi were asked to allocate rationed vouchers between anonymous citizens; some of these citizens attempted to bribe the public servants to obtain more vouchers than they were entitled to. Two groups of public servants were randomly exposed to short messages about good governance or professional identity reminders. Participants in these two groups behaved in a fairer manner than those of a third group who were not exposed to any message. The result is more robust in the case of the group exposed to the professional identity reminder. The underlying mechanisms seem to be that when a public servant reflects upon governance values and her professional identity, the moral cost increases, prompting more equal service delivery. Bribe-taking was not impacted by the messages. The experiment provides new insights into the design of anti-corruption strategies.The second chapter, written with Lena Epp, investigates the impact of a public officials’ fairness considerations towards citizens in a petty corruption situation. Other-regarding preferences, and, more particularly, fairness concerns are widely acknowledged as crucial elements of individual economic decision-making. In petty corruption contexts, public officials are to a large extent aware of differences between citizens. Here, we experimentally investigate how fairness considerations may impact on corrupt behaviour. Our novel bribery game reveals that bribes are less frequently accepted when bribers are unequal in terms of endowments. These results suggest that fairness considerations can influence corrupt behaviour.In the last chapter, I focus on political moonlighting in Wallonia. Activities outside of public office or combining specific public offices simultaneously is a topic of ongoing heated debates. An element crucial to these discussions is whether moonlighting is detrimental for politicians’ performance. In Belgium, the combination of local executive and regional legislative offices, i.e. double hat politicians, is a frequent habit for a majority of politicians. This accumulation of activities might lead to (un-)desirable outcomes in terms of political achievements. This chapter investigates the impact of holding several remunerated and honorary positions on regional MPs parliamentary activities and mayor’s municipality performance in Wallonia. I use a database of all public and private positions held by Belgian politicians in Wallonia since the disclosure of positions became compulsory for those holding at least one public position, i.e. from 2004 to 2016. For members of Parliament, wearing a double hat reduces global parliamentary activity. For mayors, it seems that holding more remunerated positions is associated with less efficient municipality management. / Doctorat en Sciences économiques et de gestion / info:eu-repo/semantics/nonPublished

Using experimentally measured temperature-process-dependent model parameters, the failure analysis and life prediction were conducted for Atmospheric Plasma Sprayed Thermal Barrier Coatings (APS-TBCs) and electron beam physical vapor deposition thermal barrier coatings (EB-PVD TBCs) with Pt-modified -NiAl bond coats deposited on Ni-base single crystal superalloys. For APS-TBC system, a residual stress model for the top coat of APS-TBC was proposed and then applied to life prediction. The capability of the life model was demonstrated using temperature-dependent model parameters. Using existing life data, a comparison of fitting approaches of life model parameters was performed. The role of the residual stresses distributed at each individual coating layer was explored and their interplay on the coating’s delamination was analyzed. For EB-PVD TBCs, based on failure mechanism analysis, two newly analytical stress models from the valley position of top coat and ridge of bond coat were proposed describing stress levels generated as consequence of the coefficient of thermal expansion (CTE) mismatch between each layers. The thermal stress within TGO was evaluated based on composite material theory, where effective parameters were calculated. The lifetime prediction of EB-PVD TBCs was conducted given that the failure analysis and life model were applied to two failure modes A and B identified experimentally for thermal cyclic process. The global wavelength related to interface rumpling and its radius curvature were identified as essential parameters in life evaluation, and the life results for failure mode A were verified by existing burner rig test data. For failure mode B, the crack growth rate along the topcoat/TGO interface was calculated using the experimentally measured average interfacial fracture toughness.

Für die Herstellung von immer kleiner werdenden elektronischen Bauteilen ist es notwendig, Schichten verschiedener Stoffe auf einem Substrat abzuscheiden. Dazu werden häufig Verfahren verwendet, bei denen Gase in kleine Strukturen eindringen und dort an der Oberfläche reagieren. Damit können Schichten abgeschieden werden. Bei der Gasströmung in mikroskopischen Strukturen auf einem Wafer zeigt sich ein anderes Strömungsverhalten als bei einer Gasströmung in einer makroskopischen Struktur bei Normaldruck. Dabei sind Kollisionen zwischen Gasteilchen oft vernachlässigbar, und die Kollisionen von Teilchen mit der Geometrie, in der sich das Gas befindet, überwiegen. Zur Untersuchung solcher Vorgänge ist es von Interesse, eine derartige Gasströmung und die entsprechenden Schichtabscheidungen simulieren zu können. In dieser Arbeit wurde ein Simulationsverfahren entwickelt, welches Gase im Bereich der freien Molekülströmung und deren chemische und physikalische Interaktionen an Oberflächen simulieren kann. Die Simulationen sind dabei speziell für die freie Molekülströmung optimiert und ist nicht auf viele Aspekte angewiesen, die in anderen Strömungsregimen notwendig sind. Dies geschieht mittels einer Monte-Carlo-Simulation von Teilchen, welche mittels Pfadverfolgung in einer beliebigen dreidimensionalen Geometrie simuliert werden können. Dabei kann eine große Menge an verschiedenen Wechselwirkungen von Teilchen mit den Wänden der Geometrie simuliert werden. Es erfolgten Vergleiche mit bekannten Literaturwerten, wie der Durchlasswahrscheinlichkeit eines Zylinders oder einem einzelnen ALD Schritt in einem zylinderförmigen Loch bei verschiedenen Adsorptionswahrscheinlichkeiten. Das verwendete Simulationsverfahren erlaubt eine einfache Erweiterung von Wechselwirkungen, welche an Oberflächen auftreten können. So wurde auch ein PVD Verfahren und der Einfluss eines Kollimators auf die Teilchenströmung untersucht.:Inhaltsverzeichnis Abbildungsverzeichnis Tabellenverzeichnis Abkürzungsverzeichnis Symbolverzeichnis 1 Motivation und Einführung 2 Grundlagen 2.1 Knudsenzahl 2.1.1 Strömungsregime 2.1.2 Mittlere freie Weglänge bei verschiedenen Teilchenarten 2.2 Schichtabscheidungen 2.2.1 Chemische Gasphasenabscheidung 2.2.2 Atomlagenabscheidung 2.2.3 Physikalische Gasphasenabscheidung 2.3 Chemische Reaktionen an Oberflächen 2.3.1 Adsorption an einer freien Oberfläche 2.4 Simulationsansätze 2.4.1 Direct Simulation Monte Carlo 2.4.2 Angular Coefficient Method 2.4.3 Pfadverfolgung von Teilchen 2.4.4 Finite Volumen Methoden 3 Modellentwicklung 3.1 Grundidee 3.2 Interaktionen an Wänden 3.2.1 Reflexion und Reemission von Teilchen 3.2.2 Chemische Reaktionen 3.2.3 Tabellierte Oberflächeninteraktionen 3.3 Erweiterung für Bereiche geringerer Knudsenzahlen 3.4 Implementation 3.4.1 Wandkollisionen 3.4.2 Raytracing und Unterteilung der Geometrie 3.4.3 Simulationsdefinition 3.4.4 Simulationen in 2D 4 Simulationen und Ergebnisse 4.1 Durchlasswahrscheinlichkeit eines Hohlzylinders 4.2 Durchlasswahrscheinlichkeit durch ein gekrümmtes Rohr in 2D 4.3 ALD in einem zylinderförmigen Loch 4.4 Gleichgewicht zwischen Adsorption und Desorption an einer Oberfläche 4.5 Sputterabscheidung von Kupfer in einem PVD-Reaktor 4.5.1 Simulationen in einem Vakuum 4.5.2 Simulation bei Verwendung eines Hintergrundgases 5 Zusammenfassung und Ausblick 5.1 Zusammenfassung 5.2 Ausblick Literaturverzeichnis Danksagung Selbstständigkeitserklärung

Master‘s thesis deals with sawing of the thin-walled parts with high speed steel slitting saw. At first the most used conventional and unconventional possibilities of materiál cutting are described by a form of search. The next chapter describes forces arising from splitting saw machining, including their dependence on a specific cutting force, a chip cross section and a engagement angle. The second part of the thesis deals with the technological improvement of the cutting process, where three possible solutions are considered – geometry of the cutting tool, PVD coating deposition of the cutting tool and process fluid change. In the experimental part non coated slitting saw with burrs, non coated deburred slitting saw and coated slitting saws are compared. Used coatings were Ti(C,N), Cr-Al-Si-N, Al-Cr-B-N, and TripleCoating Cr, which is consisting of three layers TiN + (Al,Ti)N + Cr-Al-Si-N. The experiment has shown that the cutting forces inceases as the edge radius and wear level of the cutting tool increases. Coated cuttung tools has shown lower differences between the first and the last cut. Slitting saws have been also used in real cutting process to verify experimental results.

The thesis deals with mechanical properties of thin hard wear-resistant coatings. The work presents a method of dynamic testing of thin hard coatings on a newly constructed prototype of impact wear tester. It provides a comparison with standard methods of layer testing and presents new experimental results of dynamic impact wear test of the coatings. Finally, the thesis covers preparation techniques of thin film systems deposited on various substrates and their characterization using optical and electron microscopy.

Abstract der Posterpräsentation: PVD-Beschichtungsverfahren (Physical Vapour Deposition) haben sich aufgrund der vielfältigen Möglichkeiten, unterschiedliche Oberflächeneigenschaften von dünnen Schichten mit fast jedem Volumenmaterial (Substrat) kombinieren zu können, etabliert. Durch die definierte Einstellung der Prozessparameter (z. B. Energiezufuhr, Druck, Gaszusammensetzung) können Schichten gemäß den spezifischen Anforderungen des Einsatzzweckes angepasst und optimiert werden. Selbst widersprechende Eigenschaften wie extreme Härte und Flexibilität lassen sich miteinander kombinieren. Zielsetzung des im Rahmen des BMBF-Programms „KMU-innovativ: Nanotechnologie“ (Nanochance) geförderten Forschungsvorhabens ist die Entwicklung einer neuartigen Kombination aus plasmagestützter Bogenentladung und gepulster HPPMS-Sputterabscheidung (High Power Pulsed Magnetron Sputtering) für die Herstellung von schadenstoleranten Schichten auf Umformwerkzeugen. Durch diese Kombination soll zum einen die Qualität bestehender nanokristalliner Schichtsysteme signifikant verbessert sowie eine Vielzahl neuer Schichtsysteme mit bislang nicht erreichten Eigenschaften synthetisiert werden. Ein derzeit untersuchtes Schichtsystem besteht aus einer konventionellen Hartstoffschicht mit sehr hoher Formbeständigkeit und einer weniger als fünf Mikrometer dünnen Deckschicht aus einer Cr2AlC-MAX-Phase, die chemisch und thermisch beständig ist und einen sehr geringen Reibverschleiß hat. Die Beschichtung erfolgt in einer umgerüsteten industriellen PVD-Beschichtungsanlage im Technikum der KCS Europe GmbH. Durch in-situ Plasmaanalysen sowie mikrostrukturelle und mechanische Charakterisierungen der unterschiedlich hergestellten Schichtsysteme durch die TU Dresden wird die Korrelation zwischen technischen Beschichtungsparametern, Plasmaparametern sowie Schichtstruktur und Schichteigenschaften erarbeitet. Damit wird ein tiefgreifendes Verständnis der Abscheidemechanismen von nanokristallinen Schichtsystemen und eine Beschleunigung des Entwicklungsprozesses möglich.

Stainless steel is a metal material widely used in many industries because of its high tensile strength, toughness, and corrosion resistance. Machining stainless steel is challenging due to its high work hardening tendency, low thermal conductivity, and ductility of the material resulting in built-up edge formation. Machining stainless steel at lower cutting speeds must be performed with coolant, which adds to the cost of the process and increases concerns for the environment and the operator's health and safety. Industries such as the aerospace and die-mold industries demand high-speed machining to realize productivity targets. Therefore, a cermet tool material was selected for the present study because of its high temperature resistance, high bending strength, and fracture toughness. The study focused on investigating wear mechanisms and developing a coating on a cermet tool for dry high-speed machining stainless steel to increase tool life. The wear mechanisms of tools were investigated at a fixed cutting interval in relation to the tool's composition and microstructure. Scanning Electron Microscope (SEM) was used to study the microstructure and identify elements on the tool. X-ray diffraction (XRD) was used to identify the phases and concentrations of key elements on the tool. The new advanced in-house coating was developed with Super Fine Cathode (SFC) technology on a Kobelco AIP-20 Physical Vapour Deposition (PVD) coater. The micromechanical properties of the commercial coating and in-house coatings were investigated with the help of nanoindentation and scratch tests. Atomic Force Microscopy (AFM) and SEM were used to investigate the coating microstructure and surface topography. An Alicona variable focus 3D microscope was used to investigate wear volume and wear behaviour. It was discovered that various secondary carbides used by manufacturers to manufacture cermet tools change the microstructure, which affects the machining performance of the cermet tool material. Microchipping at the depth of cut (DOC) causes catastrophic notch wear. It was found that the developed in-house coatings were able to delay the initial wear (microchipping), which improved the tool's life by 318%. This research contributes to meeting the manufacturing industry's challenging demand for dry-high speed machining with reduced manufacturing costs. / Thesis / Doctor of Philosophy (PhD) / Cutting is the process of removing unwanted material from the bulk material to obtain the desired shape. Each metal material has unique mechanical properties that lead to various machining challenges. The cutting process is done with the help of a cutting tool that wears out during the process, and a coating layer is often used to protect the tool. Stainless steel 304 is a widely used material that is difficult to machine. This study includes a systematic approach to understanding the wear mechanisms of tools and existing commercial coatings during the dry machining of stainless steel 304. An in-house coating was developed and deposited on the selected cutting tool to protect it, reduce tool wear and extend its working life. The research results will help reduce machining costs by reducing tool and coolant costs and meet the current industry demand for dry high-speed machining. It will also reduce environmental impact by reducing waste and hazardous chemicals and addressing occupational health and safety concerns.

No description available.

Les spécialistes de la gestion de projet sont partagés entre ceux qui défendent l’importance des pratiques de la GRH dans le succès global des projets et ceux qui demeurent sceptiques quant à l’existence d’une telle relation. Notre étude a pour objectif d’enrichir ce débat en tentant de confirmer ou infirmer l’existence d’une relation entre la GRH et le succès des projets dans les pays en voie de développement (PVD). La réalisation d’une étude dans les PVD, où les conditions (économiques, sociologiques, politiques, et cultuelles) sont différentes des pays industrialisés, permettra de savoir si la relation entre la GRH et le succès de projet varie en fonction des pays où le projet est implanté. Le choix de ce sujet de recherche est d’autant plus justifié que les études portant sur les facteurs de succès des projets dans les PVD, et en particulier sur la relation entre la GRH et le résultat de projets dans ses pays, sont plutôt rares. Nos résultats ont révélé que, bien que la GRH ait une relation significative avec le succès des projets dans les PVD, elle présente la corrélation la moins forte avec ce succès par rapport aux autres facteurs de succès étudiés. Ce résultat surprenant peut être expliqué essentiellement par les caractéristiques des PVD qui affectent la gestion de projet et la gestion des ressources humaines dans cette catégorie de pays. Il pourrait s’expliquer également par les caractéristiques spécifiques à la GRH dans le contexte de projet. Afin de mieux comprendre la relation entre les pratiques de GRH et le succès des projets dans les PVD, les recherches futures devraient accorder une attention particulière aux caractéristiques de la GRH propres au contexte de projet en général et au contexte de projet dans les PVD en particulier. / The specialists in the project management are divided between those who defend the importance of human resources practices in the project success and those who remain sceptics about the existence of such a relationship. Our study aims to enrich this debate and try to confirm or invalidate the existence of a relationship between the human resources management (HRM) and the project success. The realization of a study in the developing countries where the economical, social, cultural and legal conditions are different from the industrialized countries will make it possible to verify whether the relationship between the HRM and the project success would vary or not according to the countries where the project is established. Our results revealed that although the HRM has a significant relationship to the project success in the developing countries, it has the least strong correlation with this success. This surprising result can be explained essentially by the characteristics of the developing countries which affect the project management and the human resource management. This result could be also explained by the characteristics relating to the HRM in the project context. In order to better understand the relationship between the HR practices and the project success in the developing countries, future research should pay attention to the characteristics of the HRM in the project context, particularly in the developing countries.