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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.
11

Bestimmung der atomaren Struktur ultradünner Schichten auf Festkörperoberflächen mittels streifender Atomstreuung

Seifert, Jan 05 September 2012 (has links)
In dieser Dissertation wird die Struktur von ultradünnen Schichten auf atomar ebenen Festkörperoberflächen durch die streifende Streuung von Atomen und Molekülen untersucht. Dabei werden Atome mit kinetischen Energien im keV-Bereich unter flachem Einfallswinkel von etwa 1° an der Oberfläche gestreut und mit einem ortsauflösenden Detektor nachgewiesen. Bei hinreichend kleinen Projektilenergien werden Beugungserscheinungen beobachtet, die durch Interferenz von Materiewellen erklärt werden können. Die Auswertung der Intensität der Beugungsreflexe ermöglicht die Bestimmung von Atompositionen. Wird die Probe azimutal verdreht, ändern sich die seitliche Ablenkung der Projektile und die Zahl der während des Streuprozesses an der Oberfläche emittierten Elektronen. Dies wird zur Identifikation von Richtungen mit dichtgepackten Atomketten genutzt und der Vergleich mit Trajektoriensimulationen gestattet Rückschlüsse auf die Atompositionen der obersten Lage. Beim System einer Atomlage SiO2/Mo(112) kann durch mehrere Messmethoden eindeutig zwischen zwei konkurrierenden Strukturmodellen unterschieden und die Atompositionen eines Modells mit hoher Genauigkeit bestätigt werden. Die Adsorption von Sauerstoff auf einer Mo(112)-Oberfläche wird detailliert studiert und für mehrere Überstrukturphasen werden Modelle aufgestellt. Für V2O3/Au(111) kann durch Triangulationsmessungen eine geringfügige Modifikation eines existierenden Strukturmodells abgeleitet werden. Auf einer Cu(001)-Oberfläche werden dünne, kristalline FeO und Fe3O4-Schichten präpariert und untersucht. Die Inkommensurabilität der quadratischen Substrat- und der hexagonalen Adsorbateinheitszelle führt zu komplexen LEED-Mustern, die durch Mehrfachstreuung erklärt werden können. Dies ist auch der Schlüssel zur Erklärung der Beugungsbilder bei Adsorbatstrukturen der chiralen Aminosäure Alanin auf Cu(110) und damit die Grundlage für die Aufstellung eines Strukturmodells für dieses System. / In this thesis the structure of ultrathin films on atomically flat crystal surfaces is investigated by means of grazing scattering of atoms and molecules. Atoms with kinetic energies in the keV regime are scattered from the surface under small angles of incidence of approximately 1° and are detected by means of a position-sensitive detector. For sufficiently small projectile energies diffraction phenomena are observed which can be explained by interference of matter waves. The analysis of the intensities of diffraction spots makes it possible to determine atomic positions. When the sample is rotated azimuthally the deflection of projectiles and the number of emitted electrons during the scattering process at the surface varies. This is used to identify directions with close-packed strings of atoms and comparison with trajectory simulations gives information on atomic positions of the topmost layer. For the system of one atomic layer of SiO2/Mo(112) it can be unambiguously distinguished between two competing structural models. The positions of atoms of one model are confirmed with high accuracy by the use of several methods. The adsorption of oxygen on a Mo(112) surface is studied in detail and for several superstructure phases models are proposed. For the surface of a V2O3 layer on a Au(111) substrate a slight modification of an existing structural model is derived by means of triangulation measurements. On a Cu(001) surface thin crystalline FeO and Fe3O4 films are grown and studied. The incommensurability of the quadratic substrate with the hexagonal adsorbate surface unit cell gives rise to complex pattern for low energy electron diffraction, which can be explained by multiple scattering. This is also the key to the explanation of diffraction images for adsorbate structures of the chiral amino acid alanine on Cu(110) and the basis for developing a structural model for this system.
12

Etude de la déformation particule/substrat au mécanisme de liaison en projection à froid / Improvement of the coating properties deposited by cold spray and developed for different industriel applications

Xie, Yingchun 16 December 2016 (has links)
La projection à froid, aussi appelée cold spray, est considérée comme un nouveau membre de la famille de laprojection thermique depuis une trentaine d'années maintenant. Cette thèse propose d'étudier le comportement endéformation des particules et du substrat et de mettre en avant les liaisons formées dans le revêtement par deuxapproches complémentaires, expérimentale et de simulation.Une méthode innovante pour observer directement la surface fracturée des particules déposées après décollementdu substrat a été testée avec succès. Par ce moyen, la surface de contact entre particule et substrat sousdifférentes conditions a été analysée.Concernant les résultats expérimentaux, une nouvelle théorie a été proposée pour expliquer le mécanisme deliaison interfaciale d'un revêtement dur de Ni sur substrat mou d'Al reposant sur l'effet de martelage répété desparticules, sur l'effet de pression du gaz principal et sur l'effet de préchauffage du substrat. La transformation dumécanisme de liaison revêtement/substrat au cours de la construction du dépôt a été mise en évidence en passantdu verrouillage mécanique à une combinaison d'une liaison mécanique et d'une liaison métallurgique, puis à laformation d'instabilités sous forme d'un mélange tourbillonnaire à l'interface. Plus de zones de liaisonsmétallurgiques sont générées sous forte pression, une plus grande déformation plastique apparaît grâce latempérature de préchauffage, et une adhérence plus forte au sein des dépôts est capable de se produire en dépitde la présence d'un film d'oxyde épais sur la surface du substrat. / Cold spraying, also called cold gas dynamic spraying, is a new coating technology which has been developed duringthe past three decade. In this study, a comprehensive investigation on particle deformation behavior and bondingbehavior between particle and substrate was conducted by experiment and numerical method.This thesis aims at presenting an innovative method to directly observe the fractured contact surface between thecold sprayed particle and substrate. By this means, the particle/substrate fractured contact surfaces were analyzedfor different conditions.Based on the experimental results, a new theory was proposed to explain the interfacial bonding mechanism of hardNi coating onto soft Al substrate. It is assumed that the particle peening effect is essential for the formation ofdiscontinuous metallurgical bonding. The dominant coating/substrate bonding mechanism is responsible of thetransformation during the coating build-up process of the initial mechanical interlocking to a combination ofmechanical interlocking and metallurgical bonding therefore of the formation of interfacial instabilities. The highcontact pressure is the relevant factor determining the particle/substrate metallurgical bonding. More metallurgicalbonding areas were generated due to strengthen peening effect of the subsequently deposited particles with higherpropelling gas pressure. Finally, stronger adhesion is able to occur despite the presence of a thick oxide film on thesubstrate surface by the preheating of the substrate. Higher temperatures help the materials to undergoes astronger plastic deformation that disrupts the oxide films. That leads to initiate an intimate contact between particleand substrate.
13

Properties of Pt electrodes investigated by the Electrochemical Quartz Crystal Microbalance

Wang, Tao 21 November 2007 (has links)
The Electrochemical Quartz Crystal Microbalance (EQCM) was used as the main investigation tool coupled with other conventional electrochemical methods to study the electrocatalytic properties of polycrystalline Pt electrodes, including two separate projects. The first project studied the early stage of oxide film formation on the Pt surfaces and the inhibition of the catalytic properties by the oxide film. The inhibition of the fast electrode reaction of small molecules by the growth of oxide film allows those molecules to be used as probes for the nature of the oxide film. The hydrogen oxidation current, jox calculated by differencing the cyclic voltammetry currents with and without H₂ present showed a characteristic plateau-to-plateau profile, which implies a transition from the free Pt surface to the Pt surface completely covered by oxide film. This method allows determination of the onset potential for oxide formation and also the critical potential where a full monolayer of oxide is formed. This method applies to other fast surface reactions such as oxygen reduction reaction (ORR), and the results are enhanced by forced convection in the rotating disk electrode (RDE) experiments. The initial oxidation species was identified by charge and EQCM frequency analysis. Our results support the formation of a species with stoichiometry Pt₂O, for example, with an oxygen atom in the bridging position between two adjacent Pt atoms. In the second project, the stability of the Pt electrodes in acid media with Ag⁺ present was investigated. A substantial frequency drift (8.3 Hz cycle⁻¹, or 44 ng cm⁻² cycle⁻¹) was observed during Ag electrodeposition and stripping on the bare polycrystalline Pt surface. Cyclic voltammograms in pure HClO₄ solution showed nearly no frequency drift while the addition of 10⁻³ mol L⁻¹ Ag⁺ resulted in an immediate and characteristic frequency drift. The frequency drift appeared to be consistent with loss of material from the electrode surface and the ICP-MS detected a maximum Pt concentration of 2.3×10⁻⁶ mol L⁻¹ in solution due to Pt dissolution. The Pt concentration calculated from the EQCM frequency drift matched the ICP-MS results. This allowed the EQCM for direct investigation of Pt dissolution at different system temperatures, sweep rates, and potential ranges. The much higher rate of dissolution with Ag present than that in pure HClO₄ solution can be explained by the formation of Pt-Ag alloy during Ag underpotential deposition and the co-dissolution of Pt and Ag.
14

Etude des processus de corrosion du nickel par dynamique moléculaire avec un potentiel réactif ReaxFF / Study of nickel corrosion processes by molecular dynamics with reactive potential ReaxFF

Assowe Dabar, Omar 04 December 2012 (has links)
La compréhension des processus de corrosion est un élément majeur de l’étude de la durabilité des matériaux en environnements agressifs. C’est dans ce cadre que ce travail de thèse se situe. L’objectif est d’apporter un nouvel éclairage sur les processus de corrosion du nickel en milieu aqueux en utilisant la simulation par dynamique moléculaire avec un champ de force réactif « ReaxFF ».Nous nous sommes particulièrement intéressé aux réactions entres les molécules d’eau et les surfaces monocristallines de nickel. Ces résultats ont montré aucune dissociation de l’eau sur les surfaces. Par ailleurs, une adsorption des molécules en bicouche a été constatée, traduisant la polarisation mutuelle entre l’eau et le nickel, ce que confirme le calcul de charges. La surface du métal s’est chargée positivement alors que la première couche d’eau se charge négativement, reproduisant la double couche électrique. L’introduction d’un champ électrique extérieur a conditionné la réaction entre l’eau et le nickel. La présence du champ a permis d’observer les différentes étapes d’oxydation du nickel : l’adsorption des molécules d’eau puis leurs dissociations en OH- et H3O+. La dissolution des atomes de nickel à la surface puis la pénétration de O dans Ni. Ces processus d’oxydation sont répétés au cours du temps pour obtenir le film d’oxyde. L’épaisseur du film d’oxyde dépend linéairement de l’intensité du champ électrique. La cinétique d’oxydation est améliorée pour la surface (110) par rapport aux autres surfaces étudiées. L’étude de l’oxydation d’un bicristal de nickel a montré des processus identique. Par ailleurs, nous avons constaté que les premiers germes d’oxydation se sont produits au niveau des joints de grains et se sont propagés sur toute la surface. L’ensemble de ces résultats est en bon accord avec les observations expérimentales / Understanding of corrosion processes is important for the study of the durability of materials in aggressive environment. The objective is to provide new lights on the corrosion processes of nickel in aqueous condition with molecular dynamics simulation using a reactive force field "ReaxFF."We are particularly interested by the reaction between water molecules and mono-crystalline surfaces of nickel. No dissociation of water was showed on the surfaces. Moreover, an adsorption of molecules in bilayer was observed, reflecting the mutual polarization between water and nickel, which confirms the charge calculation. The metal surface is positively charged and the first water layer charged negatively, reproducing the electrical double layer. The introduction of an external electric field has conditioned the reaction between water and nickel. The presence of the field permits to observe the different stages of nickel corrosion: adsorption of water molecules, their dissociation into OH- and H3O+, the dissolution of the nickel atoms on the surface and the penetration of O in Ni. These oxidation processes are repeated over time to obtain the oxide film. The thickness of the oxide film depends linearly on the electric field intensity. The oxidation kinetics is improved to the surface (110) compared with other orientations studied. All these results are in good agreement with experimental observations
15

Sledování vývoje pevnosti mezifáze sklo-keramika při její chemické modifikaci / Strength development of glass-ceramics interphases during its chemical modification

Nowak, Petr January 2008 (has links)
Diploma thesis deals with the research of oxide interphase of ceramic composite in dependence on the amount of precursor used in sol – gel method for deposition of titanium dioxide thin layer on corundum.
16

Modeling and Spray Pyrolysis Processing of Mixed Metal Oxide Nano-Composite Gas Sensor Films

Khatami, Seyed Mohammad Navid 01 January 2014 (has links)
The role of sensor technology is obvious in improvement and optimization of many industrial processes. The sensor films, which are considered the core of chemical sensors, have the capability to detect the presence and concentration of a specific chemical substance. Such sensor films achieve selectivity by detecting the interaction of the specific chemical substance with the sensor material through selective binding, adsorption and permeation of analyte. This research focuses on development and verification of a comprehensive mathematical model of mixed metal oxide thin film growth using spray pyrolysis technique (SPT). An experimental setup is used to synthesize mixed metal oxide films on a heated substrate. The films are analyzed using a variety of characterization tools. The results are used to validate the mathematical model. There are three main stages to achieve this goal: 1) A Lagrangian-Eulerian method is applied to develop a CFD model of atomizing multi-component solution. The model predicts droplet characteristics in flight, such as spatial distribution of droplet size and concentration. 2) Upon reaching the droplets on the substrate, a mathematical model of multi-phase transport and chemical reaction phenomena in a single droplet is developed and used to predict the deposition of thin film. The various stages of droplet morphology associated with surface energy and evaporation are predicted. 3) The processed films are characterized for morphology and chemical composition (SEM, XPS) and the data are used to validate the models as well as investigate the influence of process parameters on the structural characteristics of mixed metal oxide films. The structural characteristics are investigated of nano structured thin films comprising of ZnO, SnO2, ZnO+In2O3 and SnO2+In2O3 composites. The model adequately predicts the size distribution and film thickness when the nanocrystals are well-structured at the controlled temperature and concentration.
17

Проект предприятия по производству вспомогательных материалов для литейного производства «Casting Aid» : магистерская диссертация / Project of an enterprise for the production of supporting materials for foundry

Ардышев, А. А., Пермяков, Н. А., Толмачев, М. О., Ardyshev, A. A., Permyakov, N. A., Tolmachev, M. O. January 2023 (has links)
Магистерская диссертация посвящена созданию предприятия по производству вспомогательных материалов для литейного производства, таких как керамические фильтры и экзотермические прибыли. Магистерская диссертация состоит из введения, 6 глав, заключения, списка литературы и приложений. Чтобы обеспечить высокое качество отливок, необходимо очистить металл от неметаллических включений, таких как оксидная пленка. Оксидные пленки образуются при течении металла в литниковой системе на легкоокисляемых сплавах, включая нержавеющие стали, алюминиевые сплавы. Для очистки расплава используются керамические фильтры. Была разработана линейка керамических фильтров, рассчитан состав и технология фильтров для различных сплавов, изготовлены опытные образцы. Чтобы снизить себестоимость производства отливок в рамках технологии использования химически твердеющих смесей, необходимо уменьшить размеры форм. Для этого используются экзотермические прибыли. Они нагревают расплав, позволяя уменьшить размер прибыли и, соответственно, высоту формы. Разработана линейка экзотермических прибылей, рассчитан состав и технология производства, изготовлены и испытаны опытные образцы. Проанализирована спрос на производимую продукцию. Цена продукции рассчитывается исходя из экономического эффекта от производства. Показана экономическая эффективность предприятия. / Master’s thesis is devoted to establish an enterprise for the production of supporting materials for foundry, such as ceramic filters and exothermic metal head. Master’s thesis consists of an introduction, 6 chapters, conclusion, references list and appendixes. To ensure the high quality of castings, it is necessary to clean the metal from non-metallic inclusions, such as oxide film. Oxide films occurs during the flow of metal in the feeding gate system in easily oxidizable alloys, including stainless steels, aluminum alloys. Ceramic filters are used to clean the melt. A line of ceramic filters has been developed, the composition and technology of filters for various alloys have been calculated, and prototypes have been produced. To reduce the production cost of castings within the technology of chemically bonded sand, it is necessary to reduce the size of the molds. Exothermic metal heads are used for this. It heat the melt, allowing to reduce the size of the metal head, and accordingly, the height of the mold. A line of exothermic metal heads has been developed, the composition and technology of the production have been calculated, prototypes have been produced and tested. The demand for manufactured products is analyzed. The price of products is calculated from the economic effect on production. The economic efficiency of the enterprise is shown.
18

Direct correlation of electrochemical behaviors with anti-thrombogenicity of semiconducting titanium oxide films

Wan, Guojiang, Lv, Bo, Jin, Guoshou, Maitz, Manfred F., Zhou, Jianzhang, Huang, Nan 11 October 2019 (has links)
Biomaterials-associated thrombosis is dependent critically upon electrochemical response of fibrinogen on material surface. The relationship between the response and anti-thrombogenicity of biomaterials is not well-established. Titanium oxide appears to have good anti-thrombogenicity and little is known about its underlying essential chemistry. We correlate their anti-thrombogenicity directly to electrochemical behaviors in fibrinogen containing buffer solution. High degree of inherent n-type doping was noted to contribute the impedance preventing charge transfer from fibrinogen into film (namely its activation) and consequently reduced degree of anti-thrombogenicity. The impedance was the result of high donor carrier density as well as negative flat band potential.
19

Исследование фторидной коррозии алюминиевых матриц в условиях электроэкстракции цинка : магистерская диссертация / Study of fluoride corrosion of aluminum matrices under conditions of zinc electrowinning

Рябухин, Е. А., Ryabuhin, E. A. January 2018 (has links)
Объектом исследования является фторидная коррозия алюминиевых матриц, вызывающая повышенную адгезию цинкового осадка к алюминиевому катоду. Цель работы – исследовать поведение ионов фтора при разрушении оксидной пленки алюминиевых матриц. В работе проводились термодинамическое моделирование фторсодержащих водных систем. Проведены эксперименты по изучению влияния ионов фтора на цементацию меди и цинка на алюминии. Проведены потенциометрические и гальванометрические исследования, протекающие на границе алюминий – электролит. Изучено влияние фторид-ионов на кинетику процесса разрушения оксидной пленки алюминия. Экспериментально определено влияние предварительной обработки катодов на скорость фторидной коррозии. / The object of the research is the fluoride corrosion of aluminum matrices, which causes an increased adhesion of the zinc precipitate to the aluminum cathode. The aim of this work is to investigate the behavior of fluoride ions during the destruction of an oxide film of aluminum matrices. Thermodynamic modeling of fluorine-containing water systems was carried out in the work. Studies of effect of fluoride ions on the carburization of copper and zinc on aluminum have been carried out. Potentiometric and galvanometric studies are carried out at the aluminum-electrolyte interface. The effect of fluoride ions on the kinetics of the process of destruction of an aluminum oxide film has been studied. The effect of pretreatment of cathodes on the rate of fluoride corrosion is studied experimentally.

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