Ein fragment-basierter Ansatz zur Berechnung von vertikalen Anregungsenergien in periodischen Systemen wurde entwickelt. Das Ziel war eine wellenfunktions-basierte Hierarchie von lokalen post-Hartree-Fock Methoden, welche über das weitverbreitete Ein-Elektronen Bild der Bandlücke hinausgehen und eine Möglichkeit zur systematischen Verbesserung der Ergebnisse liefern. Darüber hinaus sollte durch die Verwendung von lokalen Orbitalen eine nahtlose Einbettung des Fragments ermöglicht und eine effektive Methode für die Untersuchung von Defekten in periodischen Systemen geschaffen werden. Als erster Schritt wird das fragment-basierte Configuration Interaction Singles (CIS) Model vorgestellt. Im Anschluss erfolgt der Wechsel zum fragment-basierten lokalen algebraic-diagrammatic construction Modells zweiter Ordnung (DF-LADC(2)). Beide Methoden wurden für ein neutrales Farbzentrum in Magnesiumoxid (MgO) getestet. Dabei wurden Fragmente mit bis zu 57 Atomen verwendet. Eine Konvergenz mit der Fragmentgröße, der Größe der Superzellen und des K-mesh konnte erreicht werden. Dennoch wurde eine erste Anregungsenergie von 5.9 eV erhalten, was 0.9 eV über dem veröffentlichten experimentellen Wert liegt. Mit hoher Wahrscheinlichkeit rührt die Abweichung vom Basissatzvollständigkeitsfehler her. ”Finite-Cluster”-Berechnungen bestätigen entsprechende Basissatzfehler. Interessanterweise stimmt die erste Anregungsenergie für ein Oberflächenfarbzentrum in MgO mit einigen experimentellen Werten überein. Allerdings decken die experimentellen Werte für diese Systeme einen weiten Bereich ab (1.15 - 4.2 eV). / An embedded-fragment approach for calculation of vertical excitation energies in periodic systems has been developed. The aim is a wave-function-based hierarchy of local post-Hartree-Fock models, which goes beyond the very common one-electron picture of the band gap and offers a way for systematic improvability of the results. The use of local occupied and virtual orbitals allows for a seamless embedding model for the fragment and becomes especially effective in studying defects in solids. As a first step in the hierarchy an embedded-fragment Configuration Interaction Singles (CIS) model is presented. The second step is an embedded-fragment local algebraic diagrammatic construction scheme of second order (DF-LADC(2)). Both methods are tested for an neutral color center in bulk and surface magnesium oxide (MgO). Different fragments with up to 57 atoms were studied. A convergence with fragment size, super-cell size and k-mesh has been achieved. However a first excitation energy of 5.9 eV is obtained for the bulk MgO, which is 0.9 eV above the reported experimental value. The deviation most likely originates from the basis set incompleteness error, which, according to finite cluster studies, can be sizable. Interestingly for a surface color center in MgO the observed first excitation energy of 4.1 eV agrees with some of the experimental values (4.2 eV). However for the surface color centers in MgO the scatter of the experimental results is very large (1.15 eV - 4.2 eV).

Ce travail porte sur l'étude des propriétés optiques de l'oxyde de zinc (ZnO), matériau semi-conducteur à grand gap. La technique de caractérisation principale de ce travail est la spectroscopie par photoluminescence, technique non destructive permettant d'obtenir des informations relatives à la structure électronique d'un matériau. Après avoir présenté les propriétés du ZnO, de ses alliages, et rappelé quelques principes de base associés à la luminescence des matériaux semi-conducteurs., nous comparerons dans un premier temps les propriétés optiques de différents types de ZnO monocristallin, selon leur mode d'élaboration : matériaux massifs de différentes origines, couches épitaxiées et nanofils. Ces comparaisons ainsi que l'étude des effets sur les spectres de photoluminescence des traitements tels que recuit et passivation nous permettront d'avancer différentes hypothèses quant à l'origine de la luminescence visible dans ce matériau grand gap, sujet encore controversé dans la littérature. Dans un deuxième temps, nous présenterons notre contribution à l'étude du dopage p du matériau, qui est encore aujourd'hui le verrou pour l'obtention de diodes électroluminescentes à base de ZnO. Nous examinerons le problème du dopage intrinsèque de type n et de la compensation, préalable indispensable avant d'aborder le dopage de type p. Le dopage p est traité ici principalement au travers des études optiques d'échantillons implantés et recuits. Plusieurs variantes liées à l'implantation d'azote seront présentées et l'obtention de paires donneur accepteurs clairement mise en évidence pour des conditions de recuit optimisées. La nature des accepteurs présents est discutée par référence aux travaux antérieurs. .

Understanding the fundamentals of the growth of nanostructures is key to controlling their size and morphology. This thesis investigated the supersaturation effect as well as other effects on the growth of two one-dimensional nanomaterials - Magnesium hydroxide sulfate hydrate(MHSH) nanobelt and ZnO nanorod. It was found that the supersaturation for the growth of 1D nanomaterial had to be controlled at low level and it could be controlled through sparingly soluble carbonate salts. To examine the supersaturation effect on one-dimensional nanostructure growth, this study developed a quantitative kinetic model was developed to describe the one-dimensional nanostructure growth. The qualitative investigation and the quantitative model should provide more insight to the processes and some guide-lines for one-dimensional nanostructure growth in the future. This thesis also examines other factors such as agitation and temperature. Some other process parameters can have a significant effect on the growth process. The Zn(NO3)2 and HMT system was used as a model system to demonstrate that agitation had dramatic effects on the final morphology of the nanostructure. Spherical morphology could be obtained through mixing the reaction solution. The building blocks of the nanospheres were similar to those forming the nanorods. Thus, the spherical morphology was believed to result from the breakdown of the free diffusion of building blocks to the growing nanocrystal surface.

In present thesis, the fundamental studies on the reaction between MgO based refractories and slag were undertaken for the development of a carbon-free bonding MgO lining material. Alumina was selected as a potential binder material. Due to MgO-Al2O3 chemical reaction, the developed refractory was bonded by MgO·Al2O3 spinel phase. To begin with, an investigation of the dissolution process of dense MgO and MgO·Al2O3 spinel in liquid slag was carried out. To obtain reliable information for dissolution study, a new experimental method was therefore developed. In this method, a cylinder was rotating centrally in a special designed container with a quatrefoil profile. This method also showed a good reliability in revealing the dissolution mechanism by quenching the whole reaction system. The experimental results showed that the dissolution process of MgO and spinel was controlled by both mass transfer and chemical reaction. It was found that the rapid dissolution of spinel was mainly because of its larger driving force. To improve the resistance against slag penetration, two aspects were studied to develop carbon-free MgO refractory. First, colloidal alumina was used and the effect of its addition into MgO matrix was investigated. The use of colloidal alumina was to form bonding products in the grain boundary of MgO. The results showed that the alumina addition greatly improved the resistance of MgO based refractory against slag penetration in comparison with the decarburized MgO-carbon refractory. It was found that the improvement of resistance was mainly related to the spinel-slag reaction products of CaO·Al2O3 and CaO·MgO·Al2O3 solid phases at the grain boundaries. Second, the effect of particle size distribution on the penetration resistance of MgO was investigated. The most profound improvement against the slag penetration was obtained by using a proper particle size distribution. The results highlighted the importance of considering the refractory structure. Experiments were undertaken to investigate the dissolution mechanism of different types of MgO based refractories in liquid slag. It was observed that the dissolution of spinel bonded MgO refractory was much slower than the decarburized MgO-carbon refractory. The primary dissolution in spinel bonded MgO refractory occurred at the slag-penetrated layer, and the removal of this layer by peeling off enhanced the dissolution rate rapidly. / <p>QC 20170918</p> / European RFCS LEANSTORY project

Les surfaces minérales auraient eu un rôle important dans la chimie prébiotique, grace à leurs propriétés catalytiques, tel que le champ électrique de surface. Dans ce travail, le champ électrique à la surface de MgO et à l'interface MgO/eau est étudié en utilisant la dynamique moléculaire ab-initio. Ce champ est local et intense, de l'ordre de V/Å, même lorque la surface est recouverte d'eau. Une réaction prébiotique modèle est ensuite étudiée, à la surface de MgO : une molécule de monoxide de carbone et une molécule d'eau, donnant une molécule d'acide formique. En utilisant la métadynamique, et sans connaissance des états de transition en amont, des chemins de réaction sont trouvés et leurs profils d 'énergie libre sont calculés à 5 kcal/mol près, avec l'aide d'un échantillonage dans l'espace des configurations par « umbrella sampling ». La présence de la surface minérale stabilise l'acide formique d'au moins 15 kcal/mol par-rapport au cas en solution sans surface. La même réaction a aussi été étudiée sous un champ électrique homogène de 0,3 V/Å, afin de comparer l'effet de ce champ à l'effet du champ de surface sur le paysage d'énergie libre. Le champ homogène stabilise aussi le produit, et l'acide formique se trouve orienté dans la direction du champ électrique de surface ainsi que dans le champ électrique homogène. Ce travail montre que les conditions proche d'une surface minérale, même sans adsorption directe, peut modifier considerablement le paysage d'énergie libre de réactions chimiques, ce qui pourrait avoir de l'importance en chimie prébiotique. / Mineral surfaces are thought to be of importance to prebiotic chemistry due to their catalytic properties, which include a strong electric field at the interface. In this work the electric field at the surface of MgO and at the interface of MgO and water is studied through ab-initio molecular dynamics. The spontaneous electric field from the surface is found to be local and intense, on the order of V/Å, even when completely covered with water. A model prebiotic reaction is then studied on the model MgO surface : carbon monoxide and water yielding formic acid. Using metadynamics, reaction pathways were found with no a priori knowledge of the transition states, and umbrella sampling was then used to compute free energy landscapes to about 5 kcal/mol accuracy. The presence of the mineral surface was found to stabilise formic acid by at least 15 kcal/mol compared to the bulk case. The reaction was also studied in solution with an applied electric field of 0.3 V/Å, in order to estimate to impact of the surface electric field on the free energy landscape. The field is also found to stabilise the product, and formic acid is found to have a preferred orientation in the direction of both the applied electric field and the surface electric field. This work shows that near surface conditions (without direct adsorption) can significantly alter the free energy landscapes of chemical reactions, in a way which could be of importance for prebiotic chemistry.

Dans le manuscrit, nous étudions l'impact des défauts sur le transport électronique dépendant du spin dans les jonctions tunnel magnétiques (JTM). Ces études ont été effectuées sur des hétérostructures possédant des barrières tunnel composé de SrTiO3, TiO2 et de MgO. Dans le cas des deux premières structures, nous montrons comment l'oxydation à l'interface induit réduction très prononcée de la magnétorésistance tunnel (TMR). Dans le cas du MgO, des études optiques sur les états induits par les défauts dans la barrière isolante ont été effectué. Nous avons montré qu'il est possible de contrôler la densité de certain type de défaut (lacune d'oxygène) en altérant les conditions de dépôts du MgO. Les études électriques et optiques effectué sur ces échantillons permettent de remonter à l'énergie des défauts au sein de la barrière. Les méthodes d'analyses des mesures électrique Î (I chapeau), qui représente la variation relative ou absolue du courant électrique en fonction de la température, permet de définir différents régime de transport à travers les jonctions CoFeB/MgO/CoFeB. Le régime intrinsèque observé à basse température s'explique par les effets de structure de bande du CoFeB et du MgO (filtrages des électrons de différente symétrie par la barrière de MgO), tandis que le régime " extrinsèque " observé aux températures intermédiaires résulte d'une activation thermique progressive des lacunes d'oxygène et est accompagné d'une réduction de la résistance ainsi que du signal TMR. Nous avons également montré dans des études préliminaires qu'une excitation optique des défauts a un impact sut le magnéto-transport.

Aliar alta produtividade ao menor custo de processo é o principal desafio econômico de uma Aciaria Elétrica. Para isso, mudanças no processo almejando práticas que resultam em uma maior eficiência do FEA, com um menor custo envolvido, ocorrem constantemente. Este trabalho avalia um processo de FEA, com capacidade de 62 toneladas de aço, operando com carregamento de sucata metálica e ferro-gusa. Dois grupos de corridas de aço, pertencentes à dois cenários distintos, foram estudadas. Os cenários foram denominados Cenário I e Cenário II, sendo que, no segundo cenário ocorreram mudanças nas práticas de injeções de carbono e oxigênio, nas práticas de adição de cales no carregamento e mudanças na quantidade de Sucata Shredder no FEA. O objetivo deste trabalho foi analisar como essas mudanças influenciaram no processo. A composição química de aço e escória de dois padrões de carga (C e E) foi comparada entre os cenários. Verificou-se que a massa de escória diminuiu para os dois padrões de carga. Porém, a basicidade do padrão C foi reduzida de 2,5 para 2,1, enquanto para o padrão E manteve-se em 2,2 para os dois cenários. O MgO de saturação foi avaliado através de diagramas de saturação isotérmicos (ISD), e a maior parte das corridas do Cenário II ficaram acima da linha de saturação da escória. Houve uma redução de 30% do oxigênio injetado para os dois padrões e seus teores de fósforo no aço aumentaram significativamente. No entanto, apenas o padrão C teve uma variação nos teores de carbono no aço. A energia elétrica consumida mostrou-se dependente dos teores de FeO e MgO da escória. O padrão E apresentou um aumento significativo de 10 kWh/t. O rendimento metálico dos padrões C e E aumentou 3,59% e 2,22%, respectivamente. No Cenário II, o aumento da sucata Shredder no carregamento foi duas vezes maior. O Cenário II apresentou uma redução dos teores de cobre no aço para os dois padrões. As quantidades médias de injeção de carbono não tiveram variação significativa, por outro lado, através dos gráficos de distribuição, notou-se uma maior estabilidade nos valores de injeção. Para o padrão E observou-se uma quantidade mínima de ferro na escória para a razão global C/O de 0,75. Uma análise da razão das injeções de carbono e oxigênio durante o refino foi feita. Observou-se uma maior estabilidade das injeções ao longo do tempo de refino para o Cenário II em ambos os padrões. / Combine high productivity and lower costs is the main economical challenge of a steelmaking melt shop. Therefore, changes in the process aiming practices that result in higher efficiency of the EAF, with lower costs, occur frequently. This work evaluates an EAF process, with capacity of 62t of steel, operating with metal scrap and pig iron load. Two groups of steel heats that represents two distinct scenarios were studied. The scenarios were called Scenario I and Scenario II. In the Scenario II carbon and oxygen injection practices, limes loading practice and Shredder scrap loading amount were modified. The aim of the present work is analyze how these changes affected process parameters. The steel and slag chemical composition of two loading patterns (C and E) was compared on the scenarios. It was found that the slag mass reduces for both loading patterns. However, the basicity of the pattern C was reduced from 2.5 to 2.1 while the pattern E was maintained on 2.2 for both scenarios. The MgO saturation content of the slag is evaluated through Isothermal Solubility Diagrams. Most of the heats of the Scenario II MgO content are higher than the minimal saturation content. There was a reduction of 30% of the injected oxygen for both loading patterns and their P content increased significantly. Meanwhile, only the pattern C shows a variation on carbon content in the steel. The electric power consumption showed proportional relation to FeO and MgO content of the slag and the pattern E showed a significant increase of 10 kWh/t. The metallic yield of the patterns C and E increased 3.59 and 2.22, respectively. The scenario II showed a reduction of the Cu content in both patterns. The carbon injection amount means did not vary significantly, but, through distribution graphs, was noted a higher stability in the injection amount. For the E pattern, a minimum amount of iron in the slag was observed for the overall C/O ratio of 0,75. An analysis of the ratio of the carbon and oxygen injection during the refining period was done. It was observed a higher stability of the injections along the refining period for the Scenario II on both patterns.

In the present thesis, the correlation between ladle glaze and non-metallic inclusions in the ladle treatment was studied. A number of industrial trials with full scale ladle and laboratory works were performed to investigate the inclusions in the ladle treatment. BaO was used as tracer in the ladle slag to investigate the effect of slag on inclusion composition and the formation of non-metallic inclusions by ladle glaze. BaO was detected in the inclusions of all followed heats. This observation showed strong evidence for the generation of non-metallic inclusions by the ladle glaze. The increase of the fractions of BaO containing inclusions and their average content of BaO in the first heat with tracer suggested that the effect of slag on the composition of inclusions was a very slow process. The detachment of ladle glaze and the chemical transformations of oxide solution in the MgO matrix were investigated. The experimental results evidently showed that the ladle glaze could be the source of inclusions continually during the ladle treatment. Samples of liquid oxide solution to simulate the liquid oxide inclusions carried over from EAF were equilibrated with molten steel under controlled atmosphere. The results along with thermodynamic calculation suggested that the SiO2 content of inclusions from EAF could be considerably reduced by dissolved aluminium in the steel. This would explain the vanishing of inclusions containing high SiO2 content after deoxidation. Due to the lack of experimental data, the viscosities of slags in the Al2O3-CaO-MgO-SiO2 system were measured using the rotating cylinder method in the temperature range of 1720 to 1910 K. Eight different slag compositions related to the secondary steel making operations were selected. Viscosities in this system and its sub-systems were expressed as a function of temperature and composition based on the viscosity model developed earlier at KTH. The activities of oxide components in the Al2O3-CaO-MgO-SiO2 systems at 1873 K were measured by equilibrating liquid slag and metal. Either silicon or copper was used as the metal phase and the oxygen partial pressure was controlled with different mixing rates of Ar and CO gas flow in equilibrium with graphite. Iso-activity lines were drawn from the measured activity values in the isothermal section of the slag systems. Nine series of industrial trials were carried out using the same ladle in each series to examine the effect of ladle slag on the number of non-metallic inclusions in the next heat. It was found that the number of inclusions increased with SiO2 content of the ladle slag in the previous heat. No clear trends were found for the effects of viscosity and MgO activity of the previous slag on the number of inclusions. Theoretical analysis based on the experimental results suggested that the formation of 2CaO∙SiO2 followed but the dusting of the compound made the refractory more porous, which was reasonable for the number of non-metallic inclusions.

This dissertation presents a comprehensive study of the intrinsic room temperature ferromagnetism, RTFM, in technologically important thin films of ZnO, MgO, Mg@ZnO, the so-called d0–magnets that do not contain any intrinsic magnetic elements. We also present the first report on magnetism in Mn doped MgO films fabricated by dc magnetron sputtering. We have just published (April 2013 ‘on-line’) a state of the art review entitled ‘p-type ZnO Theory, growth, properties, and devices’ in the prestigious journal ‘Progress in Materials Science’, summarizing the recent advances of the studies on p-type ZnO thin films and pointing out the major challenges that remain in the field. The experimental work then focuses on the magnetic properties of band gap engineered Mg@ZnO films exploiting the fact that by substitutional doping of Mg for Zn in ZnO it is possible to tailor new materials with bandgap energy in the range 3.3 eV to 7.2 eV, thus extending the possibilities for new magnetic and optical device applications. In addition, we show that by doping Mn in MgO its magnetic properties can be enhanced to saturation values as high as 38.5 emu/cm3 in a 92 nm thick film. These studies involve extensive characterization of the high quality films in the thickness range of nanometers, using SQUID magnetometer for magnetic properties, XRD for structural analysis, Dual beam HRSEM/FIB and AFM for accurate film cross-sectioning and surface morphology, EDXS for elemental analysis, UV-VIS NIR for measuring the band gap of MgxZn(1-x)O films, Mg K-edge NEXAFS experiment in order to understand electronic structure of specific cations present in the thin films The origin of the observed room temperature feerromaganetism is attributed to cation vacancies and its consequences on the polarization about these vacancies in the oxides... ZnO films are promising materials for optoelectronic device applications, and the fabrications of high quality p-type ZnO and p–n junction are the key steps to realize these applications. However, reliable p-type doping of the material remains a major challenge because of the self-compensation from native donor defects (VO and Zni) and/or hydrogen incorporation. Considerable efforts to obtain p-type ZnO by doping different elements with various techniques have resulted in remarkable progress in the field both from theoretical and experimental point of view. In our paper, we discuss p-type ZnO materials: theory, growth, properties and devices, comprehensively. We first discuss the native defects in ZnO. Among the native defects in ZnO, VZn and Oi act as acceptors. We then present the theory of p-type doping in ZnO, and summarize the growth techniques for p-type ZnO and the properties of p-type ZnO materials. Experimentally, besides the intrinsic p-type ZnO grown at O-rich ambient, p-type ZnO (MgZnO) materials have been prepared by various techniques using Group-I, IV and V elements. We pay a special attention to the band gap of p-type ZnO by band gap engineering and room temperature ferro magnetism observed in p-type ZnO. Finally, we summarize the devices based on p-type ZnO materials. In presenting the current studies, we first focus on the sputtering process in order to produce high quality films. From a comparative study of RTFM, in MgO films deposited by sputtering from 99.999% pure metallic Mg, Vs MgO targets respectively on glass/Si substrates under identical ambience during deposition it is found that the metallic targets give the best magnetic properties (e.g: with maximum Ms values of ~13.75 emu/g vs ~ 4.2 emu/g respectively on Si substrates.(supplement 2). Furthermore, the Ms values are strongly film thickness dependent with Mg target while it is weakly so for films from MgO target. Also, the as deposited MgO films using metallic Mg target are found to be amorphous, while it is nanocrystalline when the films are sputtered off MgO targets. The overall Ms values are found to be dependent on the oxygen content in the atmosphere during deposition, increasing to 2.69 emu/g at a oxygen partial pressure of 40% of the total working gas pressure. On annealing to nanocrystallize these films in the temperature range 600 to 8000C strong XRD peaks corresponding to (200) orientation are observed, and Ms values decrease proportionately. (supplement 3). With the above information on studies for optimizing the effect of sputtering gas, film thickness, and oxygen partial pressure, PO2, comprehensive investigations on band gap engineering and magnetism in MgxZn(1-x)O co-sputtered thin films from Mg and Zn targets are then closely examined. The optical band gap calculated from absorption spectra shows that the band gaps of Mg-doped ZnO thin films increased linearly from 3.33 to 4.074 eV. Our studies indicate that both the magnetic properties and the band gap of the film can be tailored by tuning the film thickness and PO2 in the working gas. In summary, RTFM ordering in the thin films originates from cation vacancies which couple ferromagnetically and establish long range magnetic order. The ferromagnetic ordering in these materials is shown to arise from defects situated at the cation sites. Electronic structure studies of some selected films disclose that the unoccupied O 2p states exist and this unoccupied state results from cation vacancy (VMg). / <p>QC 20130524</p>

Les enjeux actuels pour la valorisation de dérivés de la biomasse donnent à la catalyse hétérogène basique un intérêt nouveau. Dans la mesure où des relations complexes peuvent exister entre la performance d'un catalyseur hétérogène basique et sa force déprotonante, une étude des critères qui influencent la réactivité des solides dans des réactions modèles de basicité et dans une réaction modèle de transestérification a été entreprise. Il apparaît que les réactions faisant intervenir des réactifs faiblement acides (dans notre cas, un alcène), ne peuvent être réalisées que sur des sites qui peuvent interagir fortement avec les acides de Brønsted. Ces sites ne peuvent pas être caractérisés par la force de leur interaction avec une sonde CO2, car nous avons montré que les échelles de basicité selon Lewis et selon Brønsted étaient différentes. En revanche, dans le cas de réactions faisant intervenir des acides plus forts, tels des alcools, plusieurs facteurs sont à considérer. Par exemple, dans la catalyse de la transestérification, la présence de sites pouvant réagir selon une voie acide peut augmenter la puissance catalytique des solides. Par ailleurs, cette étude a permis de dégager des tendances générales sur la structure et la réactivité basique de l'oxyde de magnésium en fonction de son recouvrement en adsorbats hydroxyles et carbonates. Quatre types de carbonates adsorbés ont pu être identifiés, ce qui a permis de mettre en évidence la formation de plans (110) après certains prétraitements. Ces plans, très réactifs, sont particulièrement intéressants pour la catalyse hétérogène basique.