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Made available in DSpace on 2015-04-01T12:17:41Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2728849 bytes, checksum: 473329771da433558aad326b78ebbb89 (MD5) Previous issue date: 2013-09-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A model was used to simulate solute distribution during rapid solidification of a system Ag-15%massCu with initial undercooling of 5 K, 10 K and 30 K. Boettinger et al (1987) measured the microsegregation profile in Ag-Cu alloys superficially treated with a focused electron beam (resolidification). In that work, they found an irregular variation for Cu concentration in cross sections of the resolidified microstructures. In some cases, the profile of concentration versus radius presented a W shape. Current models of microsegregation predict a monotonic variation the concentration depending on the cell radius, which are apparently not in accordance with the acquired measurements. The present study used a numeric model to evaluate the solidification of Ag-Cu alloy under same conditions to the Boettinger´s experiment. Numerical results are for a metallic spherical drop, initially liquid, cooled by convection. Solidification starts in the center of the droplet in a given undercooling. The algorithm used here is based on a model in volumetric average of the quantities and the balance equations in a representative elementary volume for treating a solid/liquid mixture. Inside the droplet transport of energy and mass are repurely diffusive processes of average quantities. The algorithm used permitted a global analysis of the phenomena occurring during the solidification process, as well as a local analysis of the quantities involved, which has been shown to be a prerequisite for the prediction of non-monotonic profiles of microsegregation, such as those measured in the experiment mentioned above. / Foi utilizado um modelo para simular a distribuição de soluto durante a solidificação rápida de um sistema Ag-15%Cu com superresfriamentos iniciais de 5 K, 10 K e 30 K. Boettinger et al (1987) mediram o perfil de microssegregação em ligas Ag-Cu tratadas superficialmente com um feixe de laser (resolidificação). Nesse trabalho, os autores constataram uma variação irregular para a concentração de cobre em seções transversais de células nas microestruturas resolidificadas. Em alguns casos um perfil de concentração ao longo do raio em forma de W foi medido. Os modelos de microssegregação atuais, em geral, preveem uma variação monotônica da concentração em função do raio da célula, o que aparentemente não está de acordo com as medições obtidas. No presente trabalho, foi usado um modelo numérico para avaliar a solidificação de uma liga Ag-Cu em condições análogas às do experimento de Boettinger. Os resultados numéricos são para uma gota metálica esférica, inicialmente líquida, resfriada por convecção. A solidificação tem início no centro da gota em um superresfriamento dado. O algoritmo usado foi desenvolvido previamente para um modelo baseado na tomada de médias volumétricas das grandezas e das equações de balanço descritivas em um volume elementar representativo para tratar com uma mistura sólido/líquido. No interior da gota, os transportes de energia e massa são processos puramente difusivos de grandezas médias. O algoritmo usado permite não apenas uma análise global dos fenômenos que ocorrem durante o processo de solidificação, mas também uma análise local das grandezas envolvidas, o que demonstrou ser condição necessária para a previsão dos perfis não monotônicos de microssegregação, tais como os medidos no experimento mencionado acima.

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Title: Electronics and adsorption properties of model catalytic systems contains cerium Author: Miloš Cabala Department: Department of Surface and Plasma Science, Supervisor: RNDr. Kateřina Veltruská, Department of Surface and Plasma Science, Abstract: The doctoral thesis contains the study of model catalyst systems based on cerium and ceria. The thesis deals with model systems of CeAg, CeO2/Cu(111), Ni- CeO2/Cu(111) a Ni-Sn-CeO2/Cu(111). We have studied these systems using photoelectron spectroscopy, ion scattering spectroscopy and low energy electron diffraction. Model systems were prepared under strictly defined conditions. The strong bimetallic interaction was observed on the CeAg layers. Molecular adsorption of carbon monoxide on CeAg was demonstrated. We also observed intensive reaction of these layers with oxygen. By measurements in different directions of surface Brillouin zone, we managed to reconstruct the band structure of the prepared CeO2/Cu(111) layer. We have shown that the Cu substrate interacts weakly with deposited CeO2 layer. This interaction results in a charge transfer from Cu into CeO2. Overall, in the valence spectrum we have identified three main electron bands corresponding to O 2p state bound in CeO2. It has been proven that the deposition of Ni on CeO2 layers leads to partial...

Joining of electronic components onto the circuit boards is done by soldering operation, during production of all electronic devices. In many countries, including Turkey, traditionally used tin-lead (Sn-Pb) solder alloys have been restricted to be used in consumer electronics appliances because of the toxic effects of lead (Pb) within these alloys. Tin-silver-copper (Sn-Ag-Cu) based alloys have been developed as the most promising candidate that can replace the Sn-Pb alloys. However, various problems have emerged with the increasing trend in use of Sn-Ag-Cu solder alloys in electronics industry, namely large intermetallic compound formation, low wettability and thermal shock resistance. Many researches have been done in the past decade to overcome these problems. The solutions are based on changing the undercooling of the solder alloy / which was determined to be done by either changing the composition of the solder alloy by micro-alloying or changing the cooling rate during soldering operation. In this thesis study Sn-3.5Ag-0.9Cu (wt. %) lead-free solder having the eutectic composition, was micro-alloyed with additions of aluminum (Al), iron (Fe) and titanium (Ti). Experimental results were compared with commercially available near-eutectic Sn-40Pb (wt. %) solder, a commercially available Sn-3.0Ag-0.5Cu (wt. %) solder and also eutectic Sn-3.5Ag.0.9Cu (wt. %) and near-eutectic Sn-3.7Ag-0.9Cu (wt. %) solders that were produced for this thesis study. In the first stage of the study, the effects of 0.05 wt. % of Al, Fe and Ti micro-alloying were investigated. When preliminary results of mechanical and thermal test were compared, Fe was found to make positive effect on shear strength and undercooling. Further research was carried out to establish a relationship between the Fe compositions and solder properties. Therefore, 0.01, 0.03, 0.07 and 0.1 wt. % Fe additions were also studied and results were reported. 0.01 wt. % and 0.07 wt. % Fe added solders were found to have a smaller undercooling, resulting with dispersed intermetallic compound (IMC) and thus has highest shear strength. Different cooling rates / 0.017, 0.17 and 1.7 &deg / C/sec were applied to solder-copper joints and microstructures were investigated. Large IMC-free microstructure was achieved by 0.01 wt. % Fe micro-alloyed solder, which was cooled with 1.7 &deg / C/sec rate. Wetting of copper substrate was found to be improved by additions of Al, Fe and Ti compared to alloy with eutectic composition of Sn-Ag-Cu alloy. Selected SAC+X alloys have been subjected to thermal shock experiments for crack formation analysis on the copper substrate-solder joints. The results showed that SAC+0.05Al solder has the higher thermal shock resistance, which no cracks were observed after 1500 cycles of thermal shock. In order to understand the insights of SAC performance, some of the lead-free solders were applied onto printed circuit boards for thermal shock resistance test. These results have indicate that the cracking may occur after thermal shock cycles due to process conditions of soldering operation (i.e. cooing rate), independent of the solder alloy composition.

The present thesis deals with synthesis of free alloy nanoparticles in immiscible alloy systems by the process of laser ablation under a liquid. In this process the alloy target is submerged in a liquid and the plume formed by the laser beam interaction with the target is confined in the liquid. The nanoparticles formed inside this plume and get quenched by the surrounding liquid yielding suspension of nanoparticles in the liquid. By the addition of suitable surfactants, these nanoparticles can be protected from other reactions and their size can be controlled by preventing further growth. We have selected immiscible alloys for the present study. These alloys tend to phase separate in melt as well as in solid depending on the value of the positive heat of mixing. We have used two binary alloys for the present study. These are alloys in Ag-Cu system and Fe-Cu system. In both these systems, there are reports of formation of extended solid solution due to kinetic factors during nonequilibrium processing like rapid solidification and mechanical alloying. In the present thesis we report synthesis of alloy nanoparticles of different compositions and sizes in these two systems and explore the nature of the phases that form in the small (nano) particles and their evolutionary pathways leading to the final microstructure. Microscopic techniques, especially transmission electron microscope, were used for characterization of these nanoparticles. The phase evolution was further studied using in situ microscopic techniques. After introducing the thesis in the Chapter 1, we describe briefly the relevant literatures in Chapter 2. The experimental details, in particular the experimental set up for laser ablation with targets under liquid are described in chapter 3. This chapter also includes the experimental details of the characterization. Transmission electron microscopy was used as primary characterization tool in the present study. The Chapter 4 presents the result of our study of alloy nanoparticles in Fe-Cu system. This system exhibits a submerged liquid miscibility gap. Although we have studied alloy targets of different compositions, the results of alloy nanoparticles obtained from targets with compositions Cu-40at.%Fe and Cu-60at.%Fe were primarily presented in this chapter. The nanoparticles that were synthesized had a size range of approximately 40nm to more than 100 nm. These particles have spherical morphology. The measurements of local compositions of different locations in the particle indicate the presence of a layer of Fe3O4 oxide at the spherical surface. This layer is devoid of copper. Most of the copper exist in the core of the particle. Fe rich spherical particles of much smaller size (~15 nm) are found to be embedded in the copper rich core. The copper formed solid solution with Fe and a copper concentration gradient exists in the particle below oxide layer due to oxidation of Fe. In contrast the nanoparticles obtained from alloy target with composition Fe-40at.% Cu have a spherical morphology. These have a composite structure with a Fe core in addition to Fe3O4 oxide layer at the surface. We have attempted to explain the phase evolution taking into account under cooling of the melt condensate that forms in the plume and their subsequent solidification through submerged miscibility gap. The chapters 5-7 deals with alloys of Ag-Cu system. In Chapter 5, we have carried out a detailed study of morphological evolution of the nanoparticles of Ag-Cu system. After optimizing the ablation parameters using pure Ag and Cu targets, we have synthesized alloy nanoparticles using different target compositions over the entire range of compositions with sizes having a mode of 25 nm. The evolution of the two phase structure is shown to be composition dependent with particles near equiatomic composition exhibit solid solution with uniformly distributed segregations of composition (Cu & Ag rich) while copper rich alloys exhibit a core shell structure with outer layer being Ag rich. The isothermal experiments again reveal emergence of core-shell morphology at intermediate time for particles with equiatomic composition. In order to compare the results of Ag-Cu nanoparticles with particles produced by other techniques we have synthesized Ag-Cu nanoparticles of near equiatomic composition by chemical route using nitrate salts and NaBH4 as reducing agent. PVP was used as capping agent. The results are presented in chapter 6. Depending on time of reaction, it is possible to synthesis free alloy particles from 2-3 nm to a network of chains. The nanoparticles contain Ag rich and Ag deficient region with Ag tends to segregate near surface. We have also presented mechanism for the formation of chain structure with prolonged reaction. The thermodynamic basis of phase formation in the immiscible system and evolution of phases under nonequilibrium situation have been discussed in chapter 7. This also includes a model to estimate size dependent surface energy. The analysis presented allows a discussion of possible pathways for phase evolution observed in the present work. The thesis ends with a final chapter that discussed the critical issues remains to be addressed and possible future work.

Dans ce travail nous démontrons, au travers de deux études, l'intérêt fondamental du couplage des techniques de photoémission résolue en angle (ARPES) et de spectroscopie tunnel (STS) dans l'analyse des propriétés électroniques d'interfaces nanostructurées. Dans la première partie, nous présentons une méthodologie permettant de déduire le potentiel de surface induit par la reconstruction triangulaire d'une monocouche d'Ag/Cu(111). Cette méthode est basée sur la mesure des gaps caractérisant la structure de bande de l'état de Shockley du système aux points de haute symétrie de la zone de Brillouin. L'évaporation d'adatomes de potassium permet d'augmenter le nombre de gaps accessibles en photoémission en décalant les bandes vers les états occupés. Dans un modèle d'électrons presque libres, leur amplitude nous donne accès aux premières composantes de Fourier du potentiel. La reconstruction de ce dernier dans l'espace direct nous permet ensuite de calculer la densité d'états locale que nous comparons aux mesures de conductance STS. La seconde partie est consacrée à l'étude de la croissance et des propriétés électroniques des molécules de 1,4-dibromobenzène (DBB) et 1,4-diiodobenzène (DIB) évaporées sur Cu(110). Leur dépôt à température ambiante sur la surface entraîne la déshalogénation des molécules et la formation de phases organométalliques. A 200°C, le système polymérise pour former des chaînes unidimensionnelles de poly(p-phénylène) parfaitement alignées. Les mesures ARPES révèlent l'existence d'une bande pi unidimensionnelle d'états HOMOs dispersant sous le niveau de Fermi. En STS, nous observons également, pour des petites chaînes, le confinement des états LUMOs dans la partie inoccupée du spectre. Le déconfinement de ces états pour les grandes chaînes conduit à la formation d'une bande continue croisant le niveau de Fermi, conférant au polymère un caractère métallique 1D. Le gap HOMO-LUMO est alors mesuré à 1.15 eV / In this work, through two different studies, we demonstrate the fundamental interest in the coupling of angle resolved photoemission (ARPES) and scanning tunneling spectroscopy (STS) to investigate the electronic properties of nanostructured interfaces. In the first part we present a methodology to determine the surface potential of the triangular reconstructed one monolayer of Ag/Cu(111) interface from ARPES. This method is based on the measurement of the Shockley state band structure’s gaps at the high symmetry points of the Brillouin zone. Deposition of potassium adatoms allows us to shift the surface state towards higher binding energies in order to increase the number of accessible gaps in photoemission. From the magnitude of these gaps we deduce the two first Fourier components of the potential felt by electrons using the nearly free electron model. Then we reconstruct it and calculate the local density of states in order to compare it with the conductance maps probed by STS. In the second part we report the study of the growth and the electronic properties of the two molecules 1,4-dibromobenzene (DBB) and 1,4-diiodobenzene (DIB) evaporated on Cu(110). For room temperature deposition, we first observe their deshalogenation and the formation of an intermediate organometallic phase. Then, above 200°C, the system polymerizes into a long-range ordered array of one dimensional poly(p-phenylene) polymer. ARPES intensity maps allowed us to identify a one dimensional graphene-like strongly dispersive pi-band below the Fermi energy. By STS we also observed LUMOs confined states for small chains over the Fermi level. The loss of confinement for long chains induces the formation of a continuous dispersive band which crosses the Fermi energy, conferring a 1D metallic character to the polymer. The HOMO-LUMO gap is found to be 1.15 eV