The main purpose of this thesis is to study and analyze how concepts of childhood and adolescence were constructed in scientific medicine during the period 1870 to 1930. The focus in the first part of the thesis is to study the sick girl as a stereotype in 1870–1900. In the late nineteenth-century, the poor health of girls was a popular topic in Swedish medical discourse. It was a well-established opinion that a substantial number of Swedish girls suffered from various diseases and ailments. Mass- and coeducation was under debate and physicians became interested in the impact of schools and schooling on children’s health. It is here shown that children, and in particularly adolescents, were de-fined as gendered creatures. The doctors emphasized the universal nature of adolescence and conceptualized pu-berty as a traumatic and risky stage of life and they also tended to focus on middle-class girls. Pubescent girls were seen as most vulnerable to external stress such as mental strain and physical demands. Physicians claimed that ill health inevitably followed when girls were educated in the same way as boys. However, boys and their health were discussed too. The most common ailments for both girls and boys were overstudy, anemia, headaches and disor-dered digestion. It was also shown in various studies, that poorer children were substantially inferior in weight as well as in height. Chlorosis was a common theme in late nineteenth-century medical discourse. Although it appeared mainly as a girls’ disease in medical books and in most sanitary journals, health studies for example, showed that chlorosis could also be a boys’ disease. However, sick boys were rarely spoken of. Medical opinions on overstudy, chlorosis and dress reform could be interpreted as a concern for unhealthy girls as future mothers of the nation. It is not my intention to advertise doctors as vicious oppressors, as opponents of female emancipation. In fact, the doctors often pointed out social factors and unequal circumstances of childhood and adolescence for girls and boys. In early twentieth-century, the scientific opinion of girls changed. Even though gendered notions of children and youths persisted all through the period studied, more and more some doctors, Karolina Widerström, for example, began to question them. The new girl was not weak and ill, but rather healthy and active. However, a dividing line between those who claimed the weakness of girls and those who emphasized the new, healthy girl became more evident after 1900. In this thesis, this disparity is discussed in terms of popular medical discourse and scientific medi-cal discourse. In the latter, girls were still described as more sensitive and more frail than boys and as unfit for higher education and strenuous schoolwork. Thus, the new girl – vivid, healthy and equal to the boy – was above all a con-struction in popular medicine. The uniform medical discourse on girls from the late nineteenth-century thus dissolved. A number of changes in the medical discourse on sickness and health of girls and boys during in this period occurred. First, concepts of sickness and health were modified over time and fewer schoolchildren were considered sick. Fi-nally, in the beginning of the period studied, girls were sicker than boys were, but in the end, in the 1930s, there was no obvious gender difference. Both sexes seemed equally sick (or healthy).

Les systèmes de localisations existants présentent des insuffisances au niveau desapplications en environnement indoor. Ces insuffisances se traduisent soit par la non-disponibilité des signaux (le GPS) dans ce type d’environnement, soit par leur manque de précision quand ils sont prévus à cet effet. Ces limites ont motivé la recherche de nouvelles techniques. Les transmissions Ultra-Large Bande (ULB) de par leur singularité en matière de précision et de faible puissance d’émission, s’avèrent être la meilleure réponse à la problématique ci-dessus. Nous avons donc choisi cette technique pour mettre au point un procédé de localisation endogène permettant d’assurer, avec précision, la continuité des services de localisation dans les environnements indoor. Ce procédé s’appuie sur la localisation en trois dimensions (3-D). Il utilise la technique temporelle de différenciation du temps d’arrivée (TDOA). Cette technique permet de mieux tirer profit de la bonne résolution temporelle de l’ULB et de pallier au problème de synchronisation entre l’émetteur et le récepteur. Deux techniques de transmission ULB ont été étudiées : la technique d’accès multiples par séquence directe (DS-CDMA) et la technique d’accès multiples par sauts temporels (TH-CDMA). Une autre étape importante de notre étude a été de développer un algorithme non-itératif de localisation en 3-D pour réduire le temps de calcul. En effet, l’utilisation d’un algorithme non-itératif permet d’optimiser les performances du système en termes de temps de calcul voire de coûts de consommation énergétique. Après l’étude théorique des différents blocs du système, le système a été tout d’abord simulé dans le canal Gaussien (AWGN) et les canaux IEEE.802.15.4a indoor. Il a été ensuite testé dans différents environnements réels de types laboratoires. Les résultats obtenus démontrent que l’utilisation des techniques de transmission basées sur la technologie radio impulsionnelle ULB permet d’obtenir un système de localisation en 3-D avec une précision centimétrique pour les applications indoor. / Existing positioning systems have deficiencies in applications indoor environment. These deficiencies result is the non-availability of signals (GPS) in this type of environment, either by their lack of precision when they are provided for this purpose. These limitations have led to research for novel techniques. Ultra-Wide Band (UWB) transmission techniques due to their uniqueness in terms of fine resolution and low power emission, prove to be the best answer to this problem. So we choose this technique to develop a process to ensure self location, with accuracy, continuity of location services in indoor environments. This method is based on the location in three dimensions (3-D). It uses the Time Difference Of Arrival (TDOA) technique. This technique allows to better take advantage of the high time resolution of the ULB and overcome the problem of synchronization between the transmitter and the receiver. Two UWB transmission techniques were studied: the Direct Sequence multiple access technique (DS-CDMA) and Time Hopping (TH-CDMA) multiple access technique. Another important step in our study was to develop a non-iterative positioning algorithm in 3-D to reduce the computation time. Indeed, using a non-iterative algorithm optimizes system performance in terms of computing time or cost of energy consumption. After the theoretical study of the system, the proposed positioning system was firstly simulated in Additive White Gaussian Noise (AWGN) channel and indoor IEEE.802.15.4a channels. It was then tested in various real environments types laboratories. The results obtained show that using UWB impulse radio technology transmission techniques allows to achieve a high accuracy 3-D location system in order of centimeter for applications in indoor environments.

Les orogènes collisionnels sont classiquement décrits comme le résultat de l'accrétion continentale de marges proximales. Cette accrétion conduit à la surrection des reliefs et à l'export important de produits d'érosion dans les bassins d'avant-pays qui les jalonnent. Dans ce schéma géodynamique sont alors uniquement considérés les domaines pré-orogéniques les moins déformés. Pourtant, un nombre croissant d'évidences géologiques de terrain indiquent la conservation voire la réutilisation de structures héritées de la phase extensive précédant la convergence et la collision au coeur des orogènes. À partir de l'étude géo-thermochronométrique de la bordure orientale du domaine hyper-étiré nord-pyrénéen (massif de l'Agly, Zone Nord Pyrénéenne) et de son avant-pays précoce (synclinal de Rennes-les-Bains, Bassin Aquitain), cette thèse a pour objectifs de décrire l'évolution d'une marge distale au cours des premiers stades de convergence, de quantifier les processus source-réceptacle associés et d'apporter des contraintes temporelles et paléogéographiques quant à la création des tout premiers reliefs pyrénéens issus de son inversion. Grâce à l'utilisation du multi-thermochronomètre (U-Th)/He sur zircon et apatite, deux épisodes de refroidissement sont mis en évidence dans le prisme nord-pyrénéen (Campano-Maastrichtien et Eocène), chacun d'eux synchrone d'une phase de subsidence dans le bassin d'avant-pays. J'ai ainsi pu proposer un modèle équilibré d'évolution d'une marge distale hyper-amincie par inversion de structures héritées, chevauchements de socle et sous-placage continental se matérialisant par une signature thermochronologique claire de refroidissement sans érosion au début de la convergence. L'absence d'enregistrement de refroidissement au Paléocène par l'arrêt prématuré de l'inversion précoce dans le prisme nord-pyrénéen indique l'absence significative d'érosion et la position bordière de ce prisme par rapport à un édifice déjà construit plus à l'est à cette époque. Pour caractériser cet édifice aujourd'hui disparu du fait de l'ouverture du Golfe du Lion, j'ai utilisé une approche détritique de double datation in situ (U-Th)/He - U/Pb sur zircon et mis en évidence une histoire de dénudation rapide pendant le Campano-Maastrichtien, caractéristique de la création d'une topographie précoce. Ce travail montre pour la première fois clairement la migration progressive de la déformation d'est en ouest par l'inversion de structures héritées au début de la convergence pyrénéenne, ce qui suggère l'existence d'un domaine ouvert à l'est à la fin de l'épisode extensif précédant la convergence. Cette étude met en avant le rôle de l'architecture des systèmes hyper-amincis dans la formation des orogènes collisionnels et confirme les liens étroits existant entre un orogène et ses bassins d'avant-pays. / Collisional orogens are classically described as the result of continental accretion of proximal margins. This accretion leads to the creation of relief and to the important export of erosion products in the directly adjacent foreland basins. In this geodynamic scheme, only the least deformed pre-orogenic domains are considered. However, a growing number of geological field evidences indicate the preservation or even the reuse of structures inherited from the rifting phase preceding convergence and collision within orogens. By conducting a geo-thermochronometric study of the easternmost, inverted hyperextended Aptian-Cenomanian rift system (Agly massif, North Pyrenean Zone) and the adjacent early retroforeland (Rennes-les-Bains syncline, Aquitaine Basin), this thesis aims to describe the evolution of a distal rifted margin during the first stages of convergence, to quantify the associated source-to-sink processes and to provide temporal and paleogeographic constraints regarding the creation of the very first Pyrenean reliefs resulting from inversion of the margin. Using the zircon and apatite (U-Th)/He multi-thermochronometers, I show that the Pyrenean retro-wedge records two clear phases of orogenic cooling, Late Campanian-Maastrichtian and Ypresian-Bartonian, which I relate to early inversion of the distal rifted margin and main collision, respectively. I have thus been able to propose a crustal-scale sequentially restored model for the tectonic and thermal transition from extension to peak orogenesis in the eastern Pyrenees, which suggests that both thrusting and underplating processes contributed to early inversion of the Aptian-Cenomanian rift system. The absence of Paleocene cooling record indicates little to no erosion of the Pyrenean retro-wedge, suggesting the existence of a more easterly source area supplying early retroforeland sediments at this time. To characterize this eastern edifice, which has since been destroyed by the Oligocene-Miocene opening of the Gulf of Lion, I used in situ (U-Th)/He - U/Pb double dating on detrital zircons and show rapid denudation rates during early convergence, characteristic of early topographic growth. This work shows for the first time clearly the progressive migration of deformation from east to west by inversion of inherited structures at the beginning of Pyrenean convergence. This suggests the existence of an open domain in the east at the end of the rifting phase preceding convergence. This study highlights the role of the architecture of hyper-thinned systems in the formation of collisional orogens and confirms the close links between an orogen and its foreland basins.

Analyses of nuclear reactor safety have increasingly required coupling of full three dimensional neutron kinetics (NK) core models with system transient thermal–hydraulics (TH) codes.  In order to produce results within a reasonable computing time, the coupled codes use two different spatial description of the reactor core.  The TH code uses few, typically 5 to 20 TH channels, which represent the core.  The NK code uses explicit one node for each fuel assembly.  Therefore, a spatial mapping of a coarse grid TH and a fine grid NK domain is necessary.  However, improper mappings may result in loss of valuable information, thus causing inaccurate prediction of safety parameters. The purpose of this thesis is to study the effectiveness of spatial coupling (channel refinement and spatial mapping) and develop recommendations for NK/TH mapping in simulation of safety transients.  Additionally, sensitivity of stability (measured by Decay Ratio and Frequency) to the different types of mapping schemes, is analyzed against OECD/NEA Ringhals–1 Stability Benchmark data. The research methodology consists of spatial coupling convergence study, by increasing the number of TH channels and varying mapping approaches, up to and including the reference case.  The reference case consists of one-to-one mapping: one TH channel per one fuel assembly.  The comparisons of the results are done for steady–state and transient results.  In this thesis mapping (spatial coupling) definition is formed and all the existing mapping approaches were gathered, analyzed and presented.  Additionally, to increase the efficiency and applicability of spatial mapping convergence, a new mapping methodology has been proposed.  The new mapping approach is based on hierarchical clustering method; the method of unsupervised learning that is adopted by many researchers in many different scientific fields, thanks to its flexibility and robustness.  The proposed new mapping method turns out to be very successful for spatial coupling problem and can be fully automatized allowing for significant time reduction in mapping convergence study. The steady–state results obtained from three different plant models for all the investigated cases are presented.  All models achieved well converged steady–state and local parameters were compared and it was concluded that solid basis for further transient analysis was found.  Analyzing the mapping performance, the best predictions for steady–state conditions are the mappings that include the power peaking factor feature alone or with any combination of other features.  Additionally it is of value to keep the core symmetry (symmetry feature).  The big part of this research is devoted to transient analysis.  The selection of transients was done such that it covers a wide range of transients and gathered knowledge may be used for other types of transients.  As a representative of a local perturbation, Control Rod Drop Accident was chosen.  A specially prepared Feedwater Transient was investigated as a regional perturbation and a Turbine Trip is an example of a global one.  In the case of local perturbation, it has been found that a number of TH channels is less important than the type of mapping, so a high number of TH channels does not guarantee improved results.  To avoid unnecessary averaging and to obtain the best prediction, hot channel and core zone where accident happens should be always separated from the rest.  The best performance is achieved with mapping according power peaking factors, and therefore this one is recommended for such type of perturbation. The regional perturbation has been found to be more challenging than the others.  This kind of perturbation is strongly dependent on mapping type that affects the power increase rate, SCRAM time, onset of instability, development of limit cycle, etc.  It has been also concluded that a special effort is needed for input model preparation.   In contrast to the regional perturbation, the global perturbation is found to be the least demanding transient.  Here, the number of TH channels and type of mapping do not have significant impact on average plant behaviour – general plant response is always well recreated.  A special effort has also been paid to investigate the core stability performance, in both global and regional mode.  It has been found that in case of unstable cores, a low number of TH channels significantly suppresses the instability.  For these cases number of TH channels is very important and therefore at least half of the core has to be modeled to have a confidence in predicted DR and FR.  In case of regional instability in order to get correct performance of out-of-phase oscillations, it is recommended to use full-scale model.  If this is not possible, the mapping which is a mixture of 1st power mode and power peaking factors, should be used. The general conclusions and recommendations are summarized at the end of this thesis.  Development of these recommendations was one of the purposes of this investigation and they should be taken into consideration while designing new coupled TH/NK models and choosing mapping strategy for a new transient analysis. / <p>QC 20130516</p>

Nuclear power plants provide about 11 percent of the world's electricity production. For fission process is uranium fuels used with varying percentage of enrichment 235U for most of nuclear reactors. Uranium reserves are reducing and their mining cost increases. Therefore, the thorium fuel is discussed as revolution fuel for current and future nuclear power plants. This diploma thesis deals with possibility of thorium fuel utilization at various types of nuclear reactors with a focus on light water reactors. The practical part of the thesis is focused on simulation and calculations of various uranium dioxide and thorium dioxide layers at the fuel rods. Model of WWER 440 reactor was developed for the calculations with the addition of thorium fuel. The model simulates burning out of fuel for 5 years, with monitoring of fuel behavior and tracking changes of each material. The thesis tries to define the suitable ratio and parameters of layers combination of uranium and thorium fuel. For these ratios and parameters the thesis tries to give sufficient amount of computational analyzes.

The Aegean is a classic setting for studying exhumation of high-pressure (HP) metamorphic rocks. Two end-member models are proposed to explain the uplift of these rocks: core-complex style extension along low-angle normal faults and extrusion-wedge uplift. Extrusion-wedge underplating is the mechanism that exhumed HP rocks on Evia whereas Tinos hosts several detachments varying in age from 30-9 Ma. Andros, situated between them, may be the geological manifestation of the interplay of these processes and provides an opportunity to test these models. Detachments on NW Tinos and on Andros and the enigmatic low-angle Makrotantalon Unit contact on Andros were insufficiently dated prior to this study. Geo- and thermochronometrycombined with structural observations from sampling transects in the transport direction from (1) lower plate Cycladic Blueschist Unit on Andros and Tinos, (2) middle plate Makrotantalon Unit on Andros, and (3) hanging wall Upper Unit address these issues. Maximum depositional ages from detrital zircon U-Pb geochronometry and structures reveal Paleocene-Eocene syn-HP metamorphism thrusting resulted in an inversed-age relationship between the Permian Makrotantalon Unit and the underlying Triassic-Eocene Cycladic Blueschist Unit on Andros. The Makrotantalon Unit has an internal inversed stratigraphy whereas the Cycladic Blueschist Unit on Andros and Tinos appear stratigraphically intact. Structures and zircon and apatite (U-Th)/He ages in transects from NW Tinos (~12-8 Ma) and central Andros Cycladic Blueschist Unit (~13-7 Ma) indicate rapid cooling due to exhumation associated with the Livada Detachment. Older cooling ages (~16-10 Ma) and structures in the Makrotantalon Unit indicate later brittle strain localization on the Makrotantalon Thrust contact is accommodated by rheologically weaker serpentinites and calc-schists, resulting in slivering of the footwall under the Livada Detachment on Andros. Estimated mean cooling slip rates of the Livada Detachment on Andros of ~3.8 (+1.2/-1.3) km/Myr and 2.1 (+0.2/-0.2) km/Myr on NW Tinos resulted in minimum vertical exhumations of 15 km and 4 km, respectively. The NCDS here accommodated ~12-25% of 60 km of HP-rock exhumation from ~30-7 Ma. We present a tectonic model to elucidate the evolution of the Makrotantalon Unit and the magnitude, temporal, and spatial variability of exhumation via detachments on these islands. / text

Cette thèse porte sur le développement d’une approche pratique de modélisation/simulation des systèmes solaires combinés Photovoltaïques/Thermiques PV/T. Il s’agit d’une approche basée sur un modèle d’ordre réduit en représentation d’état (ORRE). En effet, les systèmes solaires thermiques, électriques et combinés intégrés aux bâtiments possèdent des spécificités permettant de s’affranchir des méthodes numériques classiques (mécanique des fluides numérique et thermique numérique). Ces méthodes sont réputées dans le domaine de l’aérodynamique, de l’aéraulique…etc. Par contre, dans le domaine du mix-énergétique tels que celui considéré dans ce mémoire, l’application directe de ce modèle peut conduire à des dépassements des capacités mémoire ou des temps de calcul exorbitants. Une alternative est de développer des méthodes adaptées au problème physique considéré, en traitant l’aspect multi-physique toute en restant dans une taille de données raisonnable et du temps de calcul réduit. La méthodologie de modélisation consiste à réduire les dimensions des équations qui régissent le problème. En se basant sur la symétrie du système, puis en découpant le système en zones de contrôle basées sur une valeur moyenne gouvernée par les nombres adimensionnels de Biot (Bi) et de Fourier (Fo). Les résultats obtenus en fonctionnement dynamique pourront nous fournir des paramètres de sorties, plus particulièrement, les rendements électrique, thermique et la puissance de circulation du fluide caloporteur. L’avantage de l’approche proposée réside dans la simplification du modèle résultant, qui est représenté par un seul système d’équations algébriques en représentation d’état regroupant tous les éléments physiques du système en fonctionnement dynamique (conditions aux limites variables dans le temps). Ce modèle regroupe la variable fondamentale qui est la température, et les deux types de contrôle et de conception. De plus, le modèle d’ORRE est intégrable dans le fonctionnement en temps réel des systèmes PV/T intégrés aux bâtiments (PV/T-Bât) afin d’accompagner leurs régulation et gestion des flux mise en jeu. Le modèle ainsi proposé a fait l’objet d’une validation où les résultats numériques ont été comparés aux résultats expérimentaux. En effet, quatre configurations ont été étudiées et évoquées dans une approche linéaire. Les résultats obtenus montrent une cohérence tolérable entre les résultats expérimentaux, et numériques. Cette cohérence a été évaluée en termes d’incertitude entre les résultats du modèle et le cas étudié expérimentalement. Le cas d’un système non-linéaire a été également abordé. En effet, rares sont les travaux qui ont été publiés mettant en valeur les phénomènes non-linéaires dans les systèmes complexes PV/T-Bât, Ainsi, on a développé avec la même stratégie, des modèles bilinéaires qui modélise le mieux possible le comportement thermique dans les systèmes PV/T-Bât. Une étude d’optimisation du système multi-physique en introduisant une étude paramétrique est menée en terme afin d’étudier la sensibilité des paramètres sur le rendement énergétique. Cependant, les études d’optimisation paramétriques restent limitées et insuffisantes à cause de la résolution mono-objectif du problème d’optimisation, alors que notre système manifeste un comportement combiné et multi-physique de nature contradictoire. Pour ce faire, une optimisation multi-objectifs est introduite avec trois fonctions objectif en employant l’algorithme génétique NSGA-II. L’originalité de notre méthode est d’employer l’algorithme en régime dynamique afin de choisir la conception du système la plus optimale. Les résultats trouvés peuvent contribuer à améliorer la conception des systèmes PV/T-Bât et l’optimisation de leur fonctionnement / This thesis consists to develop a simplified model approach for Photovoltaic / Thermal (PV / T) combined solar system based on state-space reduced order model. The building integrated solar systems are getting high attention in these last decencies, as well as the performance increasing which require high numerical methods to improve the design and reducing the costs. In one hand, the CFD methods are useful tool to predict the energy (mechanical and thermal) of combined PV/T systems, but it requires an expensive computing capacities and exorbitant calculation times, On the other hand, the PV/T systems can generate both the electrical and thermal flows, and requires an easily and performant optimization model. An alternative is to develop methods that are adapted to the physical problem under consideration, treating the multi-physics aspect while remaining in a reasonable data size and reduced computing time. The first part of the current thesis consists to develop a mathematical model which consists of reducing the dimensions of the governed equations. Based on the symmetry of the geometry, the system is subdivided into control areas which governed by the dimensionless Biot (Bi) and Fourier (Fo) numbers. The obtained results in dynamic mode can provide output key parameters, more particularly the electrical and thermal efficiencies and the dissipated hydrodynamic power. The advantage of this approach lies in the simplification of the resulting model, which is represented by a single state-space representation that groups all the physical elements of the system into dynamic mode, i.e. in continuous variation of the boundary condition. This model groups the fundamental variable, which is the temperature, and two type parameters, which are the control parameters and the design parameters. In addition, the reduced order model can be integrated into real-time operation of building-integrated PV / T (BIPV/T) systems in order to support their regulation and management of intervening flows. In order to validate the use of our model, it is necessary to test it for several cases of Building Integrated PV/T systems (BIPV/T). For this, four major configurations were studied and discussed in a linear approach; the found results show a good agreement with experimental works. A second level has been developed as part of our thesis work, which is the non-linearity in combined PV / T and BIPV/T systems; in particular, bilinear models have been developed with the same strategy which best models the thermal behavior in BIPV/T systems. The second issue, related to Multi-physics aspect. Furthermore, in order to evaluate the sensitivity of the parameters, a parametric optimization has been made with dimensionless numbers. However, parametric optimization studies remain limited and insufficient because of the single-objective resolution of the optimization problem, whereas our system manifests a mixed and multi-physics behavior with contradictory nature. To do this, a multi-objective optimization is introduced with three objective functions using the NSGA-II genetic algorithm. The originality of our method is to use the algorithm in dynamic mode in order to choose the design of the optimal system. The found results can contribute to the design of BIPV/T systems and optimize their operation

O objetivo desta tese é analisar Operación masacre de Rodolfo Walsh à luz da reflexão sobre as relações entre literatura e testemunho. O trabalho tem como hipótese que Operación masacre pode ser lida como um romance de testemunho não só porque em suas páginas denuncia a prática da violência de Estado mas, sobretudo, porque essa violência gera o imperativo ético de escrever e a procura de uma forma narrativa. / The purpose of this thesis is to analise Operación masacre written by Rodolfo Walsh under the lights of reflection about the relations between literature and testimony. The work has as hypothesis that Operación masacre can be read as a testimony novel not only because in its pages denounces the State´s violence, but above all, because this violence generates the ethical imperative of writing and the search for a narrative form.

Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 &#176C e à 746 &#176C e uma temperatura de cristalização (Tc) à 814 &#176C e à 830&#176C. O tratamento térmico à aproximadamente 1150 &#176C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 &#176C and cristallisation temperatures, Tc, at 814 and 830 &#176C, respectively. The heat treatment at around 1150 &#176C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.

In dieser Dissertation wurden das Auftreten und die ökologische Bedeutung Vivianits in Süßwassersedimenten erforscht. Vivianit ist das am weitensten verbreitete reduzierte Eisenphosphatmineral, das sich in Gewässersedimenten bildet. Über die Mechanismen der Vivianitbildung in Sedimenten und die quantitative Rolle des Minerals für die Speicherung von Phosphor ist bisher wenig bekannt. Die neuen Erkenntnisse dieser Arbeit basieren auf der Entwicklung einer neuartigen Methode, die eine direkte Identifikation Vivianits mittels Röntgendiffraktometrie in Sedimenten erlaubte. Es gelang erstmalig, Vivianit in Oberflächensedimenten zu quantifizieren. Die vorliegende Arbeit zeigt, dass Vivianit signifikant, mit 10-40 %, zur Phosphorretention in Süßwassersedimenten beitragen kann. Die Untersuchung der Bildungsbedingungen Vivianits in unterschiedlichen Gewässersedimenten Norddeutschlands zeigte, dass das molare Schwefel zu Eisen Verhältnis des Sediments als ein wichtiger Indikator für die Bedingungen identifiziert, welche die Triebkräfte für die An- und Abwesenheit Vivianits darstellen. Eine Eutrophierung von Gewässern und der damit verbundene Anstieg der Sulfidproduktion kann dabei die Bildung Vivianits beeinträchtigen, und eine Abnahme des Phosphorbindungsvermögens des Sediments zur Folge haben. Die vorliegende Arbeit macht deutlich, dass eine artifizielle Erhöhung des Eisengehaltes des Sediments im Rahmen einer Seenrestaurierung eine Vivianitbildung induzieren kann und so langfristig zu einem erhöhten Phosphorrückhalt führt. Sättigungsberechnungen ergaben, dass ein hinsichtlich Vivianits übersättigtes Porenwasser kein sicheres Indiz für die Anwesenheit des Minerals ist. Die Berechnungen sind nicht in der Lage die kleinskaligen chemischen Bedingungen im Porenraum des Sediments abzubilden. Die Untersuchungen zeigen, dass die Bildung von Vivianit einen wichtigen Prozess der Phosphorbindung in Gewässersedimenten darstellt, der bislang jedoch weitestgehend vernachlässigt wurde. / In this thesis, the occurrence and environmental relevance of vivianite in freshwater sediments were explored. Vivianite is the most common reduced iron phosphate mineral which forms in sedimentary environments. Not much is known about the mechanisms which lead to vivianite formation in surface sediments, and about the quantitative role of vivianite in phosphorus sequestration. The development of a novel sediment preparation technique allowed the direct identification of vivianite by powder X-ray diffraction. Notably, for the first time, vivianite was quantified in surface freshwater sediments. The study examplifies that vivianite can significantly contribute to the phosphorus retention in surface freshwater sediments, accounting for 10-40 % of total sedimentary phosphorus. The exploration of vivianite in different surface freshwater sediments located in northern Germany revealed that the sedimentary sulphur to iron ratio is a valuable indicator for the conditions that are important drivers behind the formation or absence of vivianite. It has been demonstrated that eutrophication and the accompanied increase in sulphide production hampers vivianite formation, leading to a decreased phosphorus binding capacity of sediments through increased sediment sulphidization. The present study also revealed, that an iron addition as a measure of lake restoration can trigger vivianite formation, and significantly increases the long-term phosphorus retention of sediments. Pore water equilibrium calculations demonstrated that supersaturated pore water is not sufficient to predict the occurrence of the mineral in situ. Those calculations often fail to predict the occurrence of vivianite because they do not adequately represent chemical conditions within sediment microenvironments. In summary, the formation of vivianite in aquatic sediments constitutes an important process in phosphorus sequestration which has so far largely been ignored.