La fabrication d’aimants permanents nano-structurés est l’une des solutions envisagées pour remplacer les aimants actuels à base de terres rares, pour lesquelles se posent des problèmes géopolitiques et environnementaux. Dans le but d’élaborer de tels matériaux, nous avons suivi une approche bottom-up utilisant des méthodes chimiques.Nos travaux ont visé dans un premier temps à synthétiser des nanoparticules (NPs) magnétiques dures qui peuvent servir de briques élémentaires dans la fabrication d’aimants nano-structurés. Notre étude systématique sur des nanobâtonnets de cobalt (NBs Co) synthétisés par voie polyol, a montré que leur champ coercitif augmente de 3 à 7 kOe avec la diminution du diamètre et l’augmentation du rapport d’aspect structural. Des simulations micro-magnétiques ont montré qu’un mécanisme de retournement d’aimantation par nucléation-propagation de parois rendait compte des résultats expérimentaux. Des NPs bi-métalliques FePt et tri-métalliques FePtX (X = Ag, Cu, Sn, Sb) de structure CFC ont été obtenues par l’adaptation d’une synthèse organométallique ou par la réduction d’acétylacétonates métalliques. Les recuits à haute température (650°C pour FePt, 400°C pour FePtX) ont conduit à la transition de phase FePt CFC L10 et à des champs coercitifs élevés (>12 kOe). La maîtrise d’un procédé multi-étapes, impliquant la protection des NPs FePt CFC par une coquille MgO et un recuit à 850°C, a permis d’obtenir des NPs FePt L10 de taille moyenne 10 nm présentant des champs coercitifs jusqu’à 27 kOe.La seconde partie de nos travaux a porté sur l’assemblage de NPs présentant des anisotropies différentes. Deux systèmes ont été étudiés : FePt CFC+FeCo CC, FePt L10+NBs Co HCP. Dans les deux cas, le contact entre les deux types de NPs a été favorisé par l’utilisation d’un ligand bi-fonctionnel suivi d’un traitement thermique. Dans le système FePt+FeCo, le recuit à haute température (650°C), nécessaire pour obtenir la phase FePt L10, a entraîné l’inter-diffusion des phases et la quasi-disparition de la phase FeCo CC. Dans le second système FePt+Co, un comportement de spring magnet a clairement été identifié, les deux phases étant efficacement couplées. L’inter-diffusion des phases a été limitée par la température modérée du recuit (400°C). Un champ coercitif de 10 kOe a été mesuré pour une teneur en Pt de seulement 25%at., malgré la perte de la forme anisotrope des NBs Co. / The production of nano-structured permanent magnets is a promising alternative to rare earth magnets, which induced geopolitical and environmental issues. In order to elaborate such materials, we followed a bottom-up approach based on chemical methods. A first objective consisted in synthesizing hard magnetic nanoparticles (NPs) as building blocks for nano-structured magnets. The properties of cobalt nanorods (Co NRs) synthesized by the polyol process have been systematically studied. Coercive fields could be raised from 3 to 7 kOe by decreasing the diameter and improving the structural aspect ratio. Micro-magnetic simulations showed that a magnetization reversal following a nucleation and domain-wall propagation process could explain the experimental results. Bi-metallic FePt and tri-metallic FePtX (X = Ag, Cu, Sn, Sb) exhibiting the FCC structure were synthesized following two routes based on the reduction of an organometallic Fe precursor or of metallic acetylacetonates. Annealing at high temperatures (650°C for FePt, 400°C for FePtX) allowed the phase transition FCC  L10 to occur, leading to high coercive fields (>12 kOe). A multi-steps process, involving the protection of FePt NPs with an MgO shell and an annealing at 850°C, was optimized to produce L10 FePt NPs with a mean size of 10 nm and a coercivity up to 27 kOe. In the second part of our study, we worked on assemblies of NPs with different magnetic anisotropies. Two systems were studied : FCC FePt+BCC FeCo, L10 FePt+HCP Co NRs. In both cases, the contact between the two types of NPs was favored by the presence of a bi-functional ligand followed by an annealing step. Concerning the FePt+FeCo system, the high temperature annealing (650°C), required to get the L10 FePt phase, led to the inter-diffusion of the phases and to the dissolution of the BCC FeCo phase. For the FePt+Co system, a spring magnet behavior has been clearly evidenced, the two phases being efficiently coupled The inter-diffusion of the phases was limited thanks to the fairly low annealing temperature (400°C). A coercive field of 10 kOe was measured for a Pt content as low as 25%at., eventhough the Co NRs anisotropic morphology was lost

[pt] O Brasil possui um Sistema Interligado Nacional (SIN) que se baseia na geração de energia elétrica por meio de usinas hidrelétricas, térmicas, solares fotovoltaicas e eólicas. O planejamento e operação deste sistema é efetuado com base em previsões efetuadas em curto, médio e longo prazo a fim de evitar imprevistos que possam afetar o suprimento da demanda de energia elétrica em território nacional. Uma das informações consideradas fundamentais em cada uma das etapas do planejamento da operação é a carga, ou seja, a demanda por energia elétrica. Quando trabalhada em curto prazo, esta é importante para a programação diária da operação, garantindo um cenário ótimo para uso dos recursos disponíveis e, em cenário mais atual, determinação do Preço de Liquidação das Diferenças a cada hora. Quando trabalhada em médio prazo, esta funciona como base para manutenções de redes e negociações de contrato. Já em longo prazo, a previsão é importante para fornecer informações usadas como base para estratégias de expansão do Sistema. Normalmente a previsão em longo prazo é trabalhada de maneira a escalonar a curva histórica anual, mas as constantes alterações no hábito de consumo da população e a inserção de novas fontes ocasionam relevantes alterações no perfil da curva de carga diária em longo prazo, tornando necessário o planejamento não somente da expansão do sistema, mas também a forma com que este poderá ser programado. Assim, com o objetivo de propor uma ferramenta de suporte ao mercado brasileiro de energia, este trabalho propõe uma Metodologia para Geração de Cenários de Carga de Longo Prazo. O método proposto propõe uma abordagem bottom-up para previsão anual da demanda utilizando premissas de trabalhos acadêmicos recentes, propõe um método de geração de perfis específicos para suprir a escassez de dados horários detalhados no Brasil e propõe a utilização da Abordagem de Decomposição Parcial a fim de transformar as previsões anuais de demanda em curvas de carga horária. Finalizando a aplicação da Metodologia para Geração de Cenários de Longo Prazo, diferentes resultados gerados são utilizados para aplicação de simulação por Monte Carlo, sendo os intervalos de confianças gerados com base na resposta, possíveis cenários de comportamento da carga no futuro, transformando um método de previsão previamente determinístico em um previsor de cenários. Com o objetivo de demonstrar resultados da método, a Metodologia é aplicada para geração de cenários de longo prazo para a região sudeste brasileira até 2020 com base na curva histórica de 2016, apesar de ser capaz de gerar previsões para horizontes maiores, demonstrando verdadeiro potencial para se adaptar a possíveis alterações na curva de carga. / [en] Brazil has a National Interconnected System which produces and transmits electrical energy through a hydro-thermo-wind system. The planning and operation of this system is based on short, medium and long term on forecasts in order to avoid unforeseen that may affect the electricity supply in national territory. The short-term forecast is important for daily schedule of operation, certifying the resource use optimal scenario and, in a current scenario, the determination of Settlement Price for Differences at each hour. The medium-term forecast is used as a basis for network maintenance and contract negotiations. The long-term forecast is important to provide information used as basis for system expansion strategies. Usually, the long-term forecast is made staggering the annual load curve, however, the constant changes on people electrical consumption habits and insertion of new electrical generation sources cause relevant changes in daily load curve profile over the long term, making necessary not only the expansion planning, but also the way it can be programmed on long-term horizon. Thus, in order to propose a support tool to the Brazilian energy market, this work presents a Scenarios Generation Methodology. Such procedure proposes bottom-up approach as an annual demand projection provider, using assumptions of recent academic works, proposes a specific profile generation method as a way to overcome the lack of specific hourly data in Brazil. Not only that, the method also proposes Partial Decomposition Approach to adapt annual electricity demand into hourly load curves. Concluding the Scenarios Generation Methodology, future scenarios are developed by Monte Carlo simulation applied over different obtained results and confidence intervals calculated based on response are possible values of load behavior in the future, thus turning a deterministic forecasting method into a scenarios generation methodology. In order to demonstrate the Methodology application, it is used to generate long-term scenarios for the southeast Brazilian region by 2020 based on historical load curve from 2016, although it is capable of generating forecasts for larger horizons, proving true potential to adapt to possible changes on load curve.

[ES] La planificación de la distribución espacial en plantas industriales (FLP) es una de las decisiones más importantes en el contexto de la dirección de operaciones, y uno de los problemas de mayor discusión en la literatura científica enmarcada en el campo amplio de la ingeniería industrial. Sin embargo, el uso generalizado del enfoque de solución top-down tradicional, que se inicia con el diseño de la distribución del conjunto de los departamentos o celdas de trabajo que conforman el sistema de producción y prosigue con la distribución detallada al interior de éstos, parte de asunciones poco compatibles con la realidad operacional industrial que implican ciertas limitaciones para su adopción en la práctica. Esto, unido al hecho de que los modelos matemáticos empleados en la generación de alternativas de layout utilizan en su mayoría el coste de manejo de materiales como una función monoobjetivo de carácter cuantitativo, desvirtuando la naturaleza multiobjetiva del problema, acentúa un vacío que genera oportunidades de mejora en la toma de decisiones de planificación del layout en la práctica industrial. En este contexto, esta tesis doctoral, respaldada por un estudio minucioso del estado del arte y el análisis de modelos de optimización matemática de referencia, presenta un marco conceptual para la toma de decisiones de planificación del FLP desde una perspectiva multiobjetivo, y un nuevo modelo de optimización multiobjetivo no lineal entero mixto (MOMINLP) para facilitar la toma de decisiones de distribución espacial en plantas industriales metalmecánicas en entornos de demanda dinámicos mediante un enfoque de planificación bottom-up, teniendo en cuenta criterios cuantitativos y cualitativos. El modelo propuesto, denominado bottom-up mDFLP, considera tres funciones objetivo que pretenden: (1) minimizar el coste total de manejo de materiales y el coste total de reorganización, (2) maximizar el rating de proximidad subjetiva entre departamentos, y (3) maximizar el ratio de utilización de área. El modelo bottom-up mDFLP ha sido validado en una empresa del sector metalmecánico, confirmando un mejor desempeño en los valores de las funciones objetivo respecto a los obtenidos en la distribución en planta actual. / [CA] La planificació de la distribució espacial en plantes industrials (FLP) és una de les decisions més importants en el context de la direcció d'operacions, i un dels problemes de major discussió en la literatura científica emmarcada en el camp ampli de l'enginyeria industrial. No obstant això, l'ús generalitzat de l'enfocament de solució top-down tradicional, que s'inicia amb el disseny de la distribució del conjunt dels departaments o cel·les de treball que conformen el sistema de producció i prossegueix amb la distribució detallada a l'interior d'aquests, part d'assumpcions poc compatibles amb la realitat operacional industrial que impliquen unes certes limitacions per a la seua adopció en la pràctica. Això, unit al fet que els models matemàtics emprats en la generació d'alternatives de layout utilitzen en la seua majoria el cost de maneig de materials com una funció monoobjetivo de caràcter quantitatiu, desvirtuant la naturalesa multiobjectiva del problema, accentua un buit que genera oportunitats de millora en la presa de decisions de planificació del layout en la pràctica industrial. En aquest context, aquesta tesi doctoral, recolzada per un estudi minuciós de l'estat de l'art i l'anàlisi de models d'optimització matemàtica de referència, presenta un marc conceptual per a la presa de decisions de planificació del FLP des d'una perspectiva multiobjectiu, i un nou model d'optimització multiobjectiu no lineal enter mixt (MOMINLP) per a facilitar la presa de decisions de distribució espacial en plantes industrials metallmecàniques en entorns de demanda dinàmics mitjançant un enfocament de planificació bottom-up, tenint en compte criteris quantitatius i qualitatius. El model proposat, denominat bottom-up mDFLP, considera tres funcions objectiu que pretenen: (1) minimitzar el cost total de maneig de materials i el cost total de reorganització, (2) maximitzar el rating de proximitat subjectiva entre departaments, i (3) maximitzar el ràtio d'utilització d'àrea. El model bottom-up mDFLP ha sigut validat en una empresa del sector metallmecànic, confirmant un millor acompliment en els valors de les funcions objectiu respecte als obtinguts en la distribució en planta actual. / [EN] Facility layout planning (FLP) is one of the most critical decisions in operations management and one of the most discussed problems in the scientific literature framed in the broad field of industrial engineering. However, the widespread use of the traditional top-down solution approach, which starts with a block layout design phase and continues with the detailed layout within each work cell making up the production system, is based on assumptions that are not very compatible with the industrial operational reality, which implies certain limitations for its adoption in practice. This issue, together with the fact that the mathematical models used in the generation of layout alternatives mostly use the cost of material handling as a single objective function of a quantitative nature, distorting the multi-objective nature of the problem, accentuates a gap that generates opportunities for improvement in the FLP decision making process in industrial practice. In this context, this doctoral thesis, supported by a thorough study of state of the art and the analysis of benchmark mathematical optimisation models, presents a conceptual framework for FLP planning decision making from a multi-objective perspective and also a new multi-objective mixed-integer non-linear optimisation model (MOMINLP) to facilitate FLP decision making for metal-mechanical industrial plants in dynamic demand environments through a bottom-up planning approach, taking into account quantitative and qualitative criteria. The proposed model, called bottom-up mDFLP, considers three objective functions that aim to: (1) minimising the total material handling cost and the total rearrangement cost, (2) maximising the subjective closeness rating between departments, (3) maximising the area utilisation ratio. The bottom-up mDFLP model has been validated in a company from the metal-mechanical sector, confirming a better performance in the values of the objective functions than those obtained in the current plant layout. / Pérez Gosende, PA. (2022). Enfoque multiobjetivo bottom-up para la planificación dinámica de la distribución espacial en plantas industriales [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/185800 / TESIS

This study sought to investigate and to record any recurring patterns in the form and communicative impact of Shona advertisements. Motivation to carry out the study came from a realisation of a growing interest in using the Shona language for advertising and the fact that very few studies have been done on Shona advertisements. For methodology, examples of Shona advertisements were qualitatively analysed using some communications and discourse analysis approaches of the speech act theory and text linguistics. A structured interview with advertising agencies randomly selected and a questionnaire on the impact of advertisements were also used. The findings of the research included that Shona was used in advertisements in order to reach out to the majority of the Zimbabwean population. In addition, Shona was also found to have been developed enough to handle formal issues like advertisements. This finding further shows that Shona advertisements reflect an instance of diglossia leakage from Shona L(ow) to Shona H(igh). Another finding is that Shona advertisements reflect some characteristics of the Shona speech community in form. These include code-switching, slang and word- division problems. An innovation in code-switching noted in some Shona advertisements is the use of three languages, namely, English, Shona and Ndebele in one advertisement. It was also established that everything about the elements of Shona advertisements communicate. For instance, the message may be visual, tactile and olfactory. It also emerged that the Shona commercial advertisements had a presenting and a hidden agenda at the same time. To achieve this the advertisements used persuasive techniques such as advertising claims, cultural hooks and personalities as spokespersons. It was also noted that most readers of advertisements do not interpret them up to the hidden persuaders but end with the direct meaning. On the other hand the Shona advertisements that gave information such as health issues have no hidden agenda. One recommendation made is that advertisements be read and studied to raise the level of awareness about the persuasive techniques used in order to distinguish between misleading advertising and those that give useful information. Some recommendations were made for future research such as carrying out similar studies of informal Shona advertisements, advertisements by n'angas/inyangas (traditional healers), prophets and political campaigns. / African Languages / M.A. (African Languages)

This study sought to examine linguistic and discursive strategies used to construct messages reflective of the implementation of the HIV and AIDS policy for Zimbabwe of 1999 by government and private newspapers. Such analysis was perceived to be important since media content has a bearing on Zimbabweans‘ perception and attitudes regarding HIV and AIDS prevention, treatment and control. The study was aimed at comparing messages from newspapers with views by the people of Zimbabwe regarding the implementation of the policy. Findings reveal that empowerment programmes particularly those targeting women and children are lagging behind as Zimbabweans, literature and newspaper data sources testify. In addition, information sources concur that cultural (For example, stigmatisation, polygamy, religious practices, spouse inheritance) and structural (For example, patriarchy, masculinity, bureaucracy, politics) are stumbling blocks that negatively affect the implementation of the policy. Further, even though private and government newspapers do not fully agree on the portrayal of human agents, there is a general consensus between newspaper reports and Zimbabweans that people still face socio-economic and econo-political challenges that militate against the smooth implementation of the HIV and AIDS policy. Government newspapers tend to downplay aspects which reveal inadequacies of government activities. The study notes this as betrayal of use of ideological squares both by government and private newspapers whereby certain aspects regarding the implementation of the policy are either downplayed or highlighted to influence perception. The study reveals that newspaper reports used nominalisation, quantification, positive politeness, thematisation, rhematisation, intertextuality, euphemism, proverbs, idioms, action verbs, metaphors and citation of experts as linguistic and discursive strategies both for agenda setting and building purposes regarding the implementation of the HIV and AIDS policy. Other devices used particularly in the encoding of Operation Murambatsvina are, claptraps, deictic referencing, personal pronouns, adjectives and direct speech. The study attributes problems regarding the Zimbabwean HIV and AIDS intervention model to the top – down approach inherent in the policy. Hence, the call for an adoption of an unhu/hunhu/ubuntu inspired bottom – up HIV and AIDS intervention model in Zimbabwe. This would inculcate pro-family, pro-village, pro-nation/people and ―servant leadership‖ (Mangena and Chitando, 2011) values in the fight against the pandemic through the embracing of Indigenous Knowledge Systems (IKS). Unfortunately, such values largely continue to elude the radar of the current top – down HIV and AIDS intervention model cuurently in use in Zimbabwe. / African Languages / D. Litt et Phil. (African Languages)

Text in English / The study focuses on the interaction between two structures in development cooperation: the bottom-up approach of Informal Youth Groups (IYGs) and the topdown approach of International Non-Governmental Organisations (INGOs). These are considered in the theoretical context of the capability approach. In the empirical study, conducted in the cities of Amman and Zarqa in Jordan, the researcher interviewed eleven key members of IYGs to analyse their work mechanisms and criteria for co-operation. A Focus Group Discussion with members of INGOs about challenges and opportunities in co-operations with IYGs was conducted, to complement the literature review of INGO perspectives. The study provides insights into the work mechanism and co-operation criteria of IYGs. The interviewees mentioned trust between the parties and sharing vision and motivation as key requirements. Recommendations for INGOs in their work with local partners and practical steps for supporting IYGs are given. / Development Studies / M.A. (Development Studies)

Τα ομομεταλικά σύμπλοκα που περιέχουν αποκλειστικά 3d μεταλλοϊόντα, καθώς και τα ετερομεταλλικά σύμπλοκα 3d/4f μεταλλοϊόντων αποτελούν σήμερα πόλο έλξης για τους ανόργανους χημικούς, λόγω των σημαντικών μαγνητικών, οπτικών και καταλυτικών τους ιδιοτήτων. Η χημεία των πολυπυρηνικών συμπλόκων (πλειάδων) των μετάλλων μετάπτωσης της 1ης Σειράς αποτελεί σήμερα ερευνητικό πεδίο αιχμής, καθώς προκύπτει από την αλληλοεπικάλυψη των επιστημών της Χημείας, της Βιολογίας και της Φυσικής, βρίσκοντας εφαρμογές σε τομείς όπως η Βιοανόργανη Χημεία, η Χημεία των Μοριακών Υλικών και η Νανοτεχνολογία. Ιδιαίτερο ενδιαφέρον παρουσιάζουν οι μαγνητικές ιδιότητες των μοριακών πλειάδων μετά την ανακάλυψη του φαινομένου του Μονομοριακού Μαγνητισμού. Μαγνήτες Μοναδικού Μορίου, ΜΜΜ (Single Molecule Magnets, SMMs) είναι μοριακές πλειάδες οι οποίες μπορούν να διατηρούν το μαγνητικό προσανατολισμό τους, απουσία ενός μαγνητικού πεδίου, κάτω από μια συγκεκριμένη θερμοκρασία. Οι ΜΜΜ αντιπροσωπεύουν τη μικρότερη συσκευή αποθήκευσης πληροφοριών με ποικιλία δυνητικών εφαρμογών. Πολλοί ΜΜΜ των 3d μετάλλων έχουν υψηλό ολικό σπιν στη θεμελιώδη κατάσταση, αλλά υστερούν σημαντικά στο θέμα της μαγνητικής ανισοτροπίας, όπως αυτή αντικατοπτρίζεται στη μικρή τιμή της παραμέτρου σχάσης μηδενικού πεδίου D. Τα λανθανίδια διαδραματίζουν έναν ιδιαίτερο ρόλο στο Μαγνητισμό, εξαιτίας της μεγάλης μαγνητικής ροπής τους, και στις περισσότερες των περιπτώσεων, λόγω της τεράστιας μαγνητικής τους ανισοτροπίας. Στην τρισθενή τους όμως οξειδωτική κατάσταση, που είναι και η πιο σταθερή, παρουσιάζουν το μειονέκτημα της πολύ ασθενούς αλληλεπίδρασης ανταλλαγής μεταξύ των μεταλλοϊόντων, ως αποτέλεσμα της αποτελεσματικής προάσπισης των ασυζεύκτων ηλεκτρονίων των 4f τροχιακών. Το γεγονός αυτό οδήγησε στη διερεύνηση συστημάτων που συνδυάζουν 4f ιόντα με άλλα παραμαγνητικά είδη, όπως οργανικές ρίζες ή 3d ιόντα. Έτσι, η ταυτόχρονη ύπαρξη των τρισθενών λανθανιδίων (LnIII) και 3d μεταλλοϊόντων μπορεί να βελτιώσει το Μονομοριακό Μαγνητισμό των πλειάδων ένταξης οδηγώντας σε μαγνητικές ιδιότητες διαφορετικές από αυτές των 3d πλειάδων. Η Διπλωματική Εργασία μας στα πλαίσια του Μεταπτυχιακού Διπλώματος Ειδίκευσης «Αναλυτική Χημεία και Νανοτεχνολογία» αφορά τη χημεία των πλειάδων των 3d/4f- μεταλλοϊόντων. Στις προσπάθειές μας να συνθέσουμε ετερομεταλλικές πλειάδες Co ή Cu/LnΙΙΙ με υποκαταστάτες οξίμες (2-πυρίδυλο οξίμες, 2,4-πεντανιοδιόνη διοξίμη) και τη δι-2-πυρίδυλο κετόνη και τα παράγωγά της, απομονώσαμε και χαρακτηρίσαμε οικογένειες συμπλόκων μεταβάλλοντας κάθε φορά παραμέτρους της αντίδρασης, όπως τη φύση του οργανικού υποκαταστάτη, τον διαλύτη της αντίδρασης, την πηγή των μεταλλοϊόντων, τη θερμοκρασία, την πίεση, κ.α. Ως συνθετική πορεία χρησιμοποιήσαμε την “bottom-up” προσέγγιση. Η στρατηγική “bottom-up” χρησιμοποιεί τις χημικές ιδιότητες των διακριτών μορίων για να προκαλέσει: Α) Αυτο-οργάνωση ή αυτο-συναρμολόγηση σε μια χρήσιμη διαμόρφωση. Β) Οργάνωση σε συγκεκριμένη θέση. Η στρατηγική αυτή χρησιμοποιείται για τις έννοιες της μοριακής αυτο-οργάνωσης ή/και της μοριακής αναγνώρισης. Σε ευρύτερο επίπεδο, δηλαδή η “bottom-up” τεχνική δυνητικά μπορεί να παράγει παράλληλες συσκευές με πολύ φθηνότερους τρόπους σε σχέση με την “top-down” μέθοδο που χρησιμοποιείται ευρέως στη σύνθεση τεχνολογικού ενδιαφέροντος συσκευών. Η μοριακή αυτή προσέγγιση ξεκινά με χρήση πηγών ανεξάρτητων ατόμων ή μικρών μορίων για τη σύνθεση μεγάλων μοριακών νανοδομών με επιθυμητές και στοχευμένες ιδιότητες, με αποτέλεσμα να αναπτύσσεται το πεδίο της Ναντεχνολογίας. Δύο γενικές προσεγγίσεις για τη σύνθεση συμπλόκων Co ή Cu/LnIII είναι: η στρατηγική που βασίζεται στη χρησιμοποίηση «μεταλλικών συμπλόκων ως υποκαταστατών» και η στρατηγική που βασίζεται στην «απλή ανάμιξη των συστατικών». Στην παρούσα Διπλωματική Εργασία εφαρμόζεται η δεύτερη κατά σειρά προσέγγιση για την παρασκευή των παρακάτω συμπλόκων ενώσεων: [CoIII {(py)C(Η)NO}2{(py)C(Η)NOH}](ClO4) [CoIII2DyIII{(py)C(Η)NO}6(H2O)(DMF)](ClO4)3.3.2H2O [CoIII2GdIII{(py)C(Η)NO}6(H2O)(DMF)](ClO4)3.3.2H2O [CoIII2DyIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2GdIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2SmIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2TbIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIIIDyIII{(py)C(Ph)NO}3(NO3)3] [CoIIIEuIII{(py)C(Ph)NO}3(NO3)3] [CoIIISmIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIIITbIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIIIGdIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIII2Na{(py)C(Η)NO}6].(OMe) [CoIII2DyIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2GdIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2TbIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2PrIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2YIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [Cu2(diba)4(κινοξαλίνη)]n [Cu3Dy2{(py)2CO2}{(py)2CO(OMe)}3{(py)2CO(OEt)}(NO3)4(H2O)2](ClO4)(OH) [Cu6{(py)2CO(OMe)}6(NO3)2](ClO4)4 [Cu3{(py)2C(OMe)(OH)}2{(py)2C(OMe)O}2(ClO4)2] (ClO4)2 .2MeOH [Cu{(py)2C(OH){CH2COCH3)}2](NO3)2.2H2O Οι δομές των συμπλόκων προσδιορίσθηκαν με Κρυσταλλογραφία Ακτίνων Χ Μονοκρυστάλλου. Σε επιλεγμένα σύμπλοκα από αυτά που συνθέσαμε μελετώνται οι μαγνητικές τους ιδιότητες. Τα σύμπλοκα χαρακτηρίστηκαν με φυσικές και φασματοσκοπικές τεχνικές. Τα δεδομένα μελετήθηκαν σε σχέση με τις γνωστές δομές των συμπλόκων και των τρόπων ένταξης των υποκαταστατών. / Homometallic complexes which contain exclusively 3d metal ions and heterometallic complexes with 3d/4f metal ions attract, nowdays, the intense interest of inorganic chemists, due to their important magnetic, optical and catalytical properties. The chemistry of polynuclear complexes (clusters) of the 1st row transition metals is a cutting-edge research area, since combines the sciences of Chemistry, Biology and Physics with applications in the fields of Bioinorganic Chemistry, Chemistry of Molecular Materials and Nanotechnology. After the discovery of the phenomenon of Single Molecule Magntesism, the magnetic properties of molecular clusters are a growning research field. Single Molecule Magnets (SMMs) are molecular clusters which can retain their magnetic orientation, in the absence of a magnetic field, below a certain temperature. SMMs represent the smallest information storage devices with multiple potential applications. Many SMMs of 3d metals exhibit high total spin in the ground state, but their disadvantage is the low value of Zero Field Splitting (ZFS) parameter, D. Lanthanides play an important role in Magnetism, due to their large spin and in most cases huge magnetic anisotropy. In their trivalent oxidation state, which is the most stable, they have the disadvantage of the very weak exchange interactions between the metal ions, as a result of the efficient shielding of unpaired 4f electrons. This fact has led to the investigation of systems combining 4f-metal ions with other paramagnetic species, such as organic radicals or 3d-metal ions. Thus, the simultaneous presence of trivalent lanthanides (LnIII) and 3d metal ions can improve the Single Molecule Magnetism behavior of coordination clusters leading to magnetic properties different from those of 3d clusters. Our Diploma Work in the context of the M.Sc. in “Analytical Chemistry and Nanotechnology” concerns the chemistry of 3d/4f clusters. In our efforts to synthesize heterometallic clusters of Co or Cu/LnIII with oximes (2-pyridyl oximes, 2,4-pentanedione dioxime) and di-2-pyridyl ketone as ligands, we have isolated and characterized new families of complexes, studying various reaction parameters, such as the nature of the organic ligand, the solvent of the reaction, the source of the metal ions, the temperature, the pressure etc. As synthetic route, we have used the “bottom-up” approach. The “bottom-up” approach uses the chemical properties of discrete molecules in order to cause: a) Self-organization or Self-assembly in an interesting configuration. b) Assembly with a specific stereochemistry. This strategy is used for the concepts of molecular self-organization and/or molecular recognition. Hence in a broader sense, the “bottom-up” approach can produce potential applications in devices with cheaper ways in relation to the “top-down” approach which is used widely for the synthesis of devices with technological interest. This molecular approach begins with the use of independent sources of atoms or small molecules for the synthesis of large molecular nanostructures with preferential and targeted properties, developing though the field of Nanotechnology. Two general synthetic approaches for the synthesis of Co or Cu/LnIII complexes are: the strategy which is based on the use of “metal complexes as ligands” and the strategy based on the “simple mixing of components”. In this Diploma Work we have used the second approach for the synthesis of the below mentioned complexes: [CoIII {(py)C(Η)NO}2{(py)C(Η)NOH}](ClO4) [CoIII2DyIII{(py)C(Η)NO}6(H2O)(DMF)](ClO4)3.3.2H2O [CoIII2GdIII{(py)C(Η)NO}6(H2O)(DMF)](ClO4)3.3.2H2O [CoIII2DyIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2GdIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2SmIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIII2TbIII{(py)C(Η)NO}6(H2O)(MeOH)](ClO4)3.3.2H2O [CoIIIDyIII{(py)C(Ph)NO}3(NO3)3] [CoIIIEuIII{(py)C(Ph)NO}3(NO3)3] [CoIIISmIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIIITbIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIIIGdIII{(py)C(Ph)NO}3(NO3)3].0.3MeOH [CoIII2Na{(py)C(Η)NO}6].(OMe) [CoIII2DyIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2GdIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2TbIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2PrIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [CoIII2YIII2{(py)C(Η)NO}4(piv)4(NO3)4].2MeCN [Cu2(diba)4(quinoxaline)]n [Cu3Dy2{(py)2CO2}{(py)2CO(OMe)}3{(py)2CO(OEt)}(NO3)4(H2O)2](ClO4)(OH) [Cu6{(py)2CO(OMe)}6(NO3)2](ClO4)4 [Cu3{(py)2C(OMe)(OH)}2{(py)2C(OMe)O}2(ClO4)2] (ClO4)2 .2MeOH [Cu{(py)2C(OH){(CH2COCH3)}2](NO3)2.2H2O The structures of the complexes have been solved with Single Crystal X-ray Crystallography. The magnetic properties of selected compounds are investigated. The complexes have been characterized by several physical and spectroscopic techniques. The data are discussed in terms of the known structures of the complexes and the coordination modes of the ligands.

This study sought to investigate and to record any recurring patterns in the form and communicative impact of Shona advertisements. Motivation to carry out the study came from a realisation of a growing interest in using the Shona language for advertising and the fact that very few studies have been done on Shona advertisements. For methodology, examples of Shona advertisements were qualitatively analysed using some communications and discourse analysis approaches of the speech act theory and text linguistics. A structured interview with advertising agencies randomly selected and a questionnaire on the impact of advertisements were also used. The findings of the research included that Shona was used in advertisements in order to reach out to the majority of the Zimbabwean population. In addition, Shona was also found to have been developed enough to handle formal issues like advertisements. This finding further shows that Shona advertisements reflect an instance of diglossia leakage from Shona L(ow) to Shona H(igh). Another finding is that Shona advertisements reflect some characteristics of the Shona speech community in form. These include code-switching, slang and word- division problems. An innovation in code-switching noted in some Shona advertisements is the use of three languages, namely, English, Shona and Ndebele in one advertisement. It was also established that everything about the elements of Shona advertisements communicate. For instance, the message may be visual, tactile and olfactory. It also emerged that the Shona commercial advertisements had a presenting and a hidden agenda at the same time. To achieve this the advertisements used persuasive techniques such as advertising claims, cultural hooks and personalities as spokespersons. It was also noted that most readers of advertisements do not interpret them up to the hidden persuaders but end with the direct meaning. On the other hand the Shona advertisements that gave information such as health issues have no hidden agenda. One recommendation made is that advertisements be read and studied to raise the level of awareness about the persuasive techniques used in order to distinguish between misleading advertising and those that give useful information. Some recommendations were made for future research such as carrying out similar studies of informal Shona advertisements, advertisements by n'angas/inyangas (traditional healers), prophets and political campaigns. / African Languages / M.A. (African Languages)

[pt] O comportamento do consumo de energia elétrica do setor industrial tem sido amplamente investigado ao longo dos últimos anos, devido a sua importância econômica, social e ambiental. Mais especificamente, o consumo de eletricidade dos subsetores da indústria brasileira exerce grande importância para o sistema energético brasileiro. Neste contexto, as projeções de longo prazo do seu consumo de energia elétrica para um país ou uma região são informações de grande relevância na tomada de decisão de órgãos e entidades que atuam no setor energético. A abordagem bottom-up determinística tem sido utilizada para obter a previsão de longo prazo em diversas áreas de pesquisa. Neste trabalho, propõe-se uma metodologia que combina a abordagem bottom-up com os modelos lineares hierárquicos para a previsão de longo prazo considerando os cenários de eficiência energética. Além disso, foi utilizada a inferência bayesiana para a estimação dos parâmetros do modelo, permitindo a incorporação de incerteza nessas previsões. Os resultados utilizando os dados de consumo de eletricidade de subsetores da indústria brasileira mostraram que a metodologia proposta consegue capturar a tajetória do consumo de eletricidade, em particular, dos subsetores de papel e celulose, e de metais não-ferrosos e outros de metalurgia. Por exemplo, os intervalos de credibilidade de 95 por cento construídos a partir do modelo estocástico contemplam os valores reais observados nos anos de 2015 e 2016. / [en] The electricity consumption behaviour in the Brazilian industry has been extensively investigated over the past years due to its economic, social and environmental importance. Specifically, the electricity consumption of the subsectors of Brazilian industry have great importance for the Brazilian energy system. In this context, the long-term projections of energy consumption of a country or region are highly relevant information to decision-making of organs and entities operating in the energy sector. The deterministic bottom-up approach has been used for the long-term forecast in several areas of research. In this paper, we propose a methodology that combines the bottom-up approach with hierarchical linear models for long-term forecasting considering energy efficiency scenarios. In addition, Bayesian inference was used to estimate the parameters of the model, allowing the uncertainty incorporation in these forecasts. The results using the electricity consumption data from subsectors of the Brazilian industry showed that the proposed methodology is able to capture the trajectory of their electricity consumption, in particular of the pulp and paper, and of non-ferrous metals and other metallurgical subsectors. For example, the 95 percent credibility intervals constructed from the stochastic model contemplate the actual values observed in the years 2015 and 2016.

Le mémoire vise à proposer une épistémologie pragmatique de la science scolaire à l’école primaire. Un défaut de compréhension de la nature de la science pourrait en effet justifier en partie les difficultés de l'enseignement des sciences par démarche d'investigation. Une étude des représentations de la science chez les enseignants et futurs enseignants confirme qu’ils n‘en ont pour la plupart qu‘une vision assez floue, relevant majoritairement d'une forme d'empirisme naïf. Un jeu opératoire de critères de scientificité adapté au contexte de l’école est développé dans une approche "bottom-up" partant des pratiques de classe effectives. Sa capacité à discriminer pratiques scientifiques et non scientifiques est discutée, de même que les implications didactiques et épistémologiques de son utilisation. Il est en particulier possible d‘en déduire des définitions évolutives d‘une science scolaire normative mais subsidiaire par rapport à la “science des scientifiques”. Cet outil épistémologique s’avère bien reçu par les enseignants auxquels il a été présenté. Le test en situation de différentes stratégies pédagogiques fait apparaître que les plus efficaces pour l'appropriation de critères de scientificité ajoutent à la démarche d’investigation une composante épistémologique explicite. Certains éléments de méthode scientifique peuvent être travaillés dès la Grande Section de maternelle (5-6 ans) : des élèves ayant vécu des démarches d’investigation s’avèrent capables de revendiquer la primauté de l’expérience, mais aussi de mettre en œuvre des tests relatifs à plusieurs critères de scientificité et de s‘approprier les rudiments de la modélisation scientifique. / The purpose of this thesis is to propose a pragmatic epistemology of school science in primary school. Indeed, some of the difficulties encountered by inquiry-based science education may be attributed to a lack of understanding of the very nature of science. A survey on the perception of science by incumbent teachers and teachers in training confirms that most of them have a relatively vague vision grounded in a form of naive empiricism. A practical set of criteria of scientificity adapted to the school context is developed through a “bottom-up” approach based on actual classroom practices. Its efficiency at discriminating scientific and non-scientific practices is discussed, as well as the didactical and epistemological implications of its use. It is thus possible to deduce evolutive definitions of a school science that is normative yet subordinated to the “science of scientists”. Teachers responded positively to this epistemological tool when it was presented to them. Among the different teaching strategies tested in a classroom, the most efficient for the acquisition of criteria of scientificity were those which supplemented the inquiry process with an explicit epistemological component. Some elements of scientific method can be introduced as early as kindergarten (5-6 y.o) : after experimenting with inquiry processes, pupils have proved able not only to claim the primacy of experiment but also to run tests related to different criteria of scientificity and acquire the basics of scientific modeling.