The efficiency of multicrystalline (mc) silicon solar cells depends strongly on the fraction of recombination active crystal defects. This work focuses on a systematic analysis of how the area fraction of recombination active crystal defects and thus the solar cell efficiency is af-fected by the grain structure of mc-silicon wafers, i.e. grain size, grain orientation and type of the grain boundaries between adjacent grains. For that purpose a new characterization method was developed which allows the measurement of the grain orientation and grain boundary type of full 156x156 mm² mc-silicon wafers. The results of the grain structure analysis were correlated with the etch pit density, the recombination active area fraction measured by photo-luminescence imaging, and the solar cell efficiency in order to quantify the most important features of the grain structure, which were relevant to obtain high quality mc-silicon wafer material. For the determination of the grain orientation and grain boundary type two metrology sys-tems were combined. The so-called grain detector determines the geometrical data of each grain (size and form) by a reflectivity measurement. Afterwards the wafer with the geomet-rical information of all grains is transferred into the so-called Laue Scanner. This system irra-diates each grain larger 3 mm² with white x-rays and creates a backscatter diffraction pattern (Laue pattern) for each grain. From this Laue pattern the grain orientation and the grain boundary type of neighboured grains is calculated and statistically analysed in combination with the geometrical data of the grain detector. In this work the grain structure of twelve industrially grown mc-silicon bricks, which were produced by different manufacturers, and two laboratory grown bricks were investigated. Seven of these bricks show a fine grain structure. This material named class F is considered to be typical for so-called High Performance Multi (HPM) silicon. The other bricks show a coarse-grained structure. This grain structure was called class G and corresponds to the con-ventional mc-silicon material. The results show that the grain structures of the start of the crystallization process differ sig-nificantly between class F and class G. The class F mc-silicon wafers have a uniform initial grain size (characterized by coefficient of variation CV¬KG < 2.5) and grain orientation (charac-terized by coefficient of variation CVKO < 1.5) distribution with a small mean grain size (< 4 mm²) and a high length fraction of random grain boundaries (> 60 %) in comparison to the class G wafers. Despite the totally different initial grain structure for the class F and class G bricks, the grain structure of the wafers which represent the end of the crystallization process is more or less comparable. It can be concluded that the development of the grain structure along the crystal height of the class F bricks is driven by an energy minimization due to the surface energy and the grain boundary energy, that means that the share of (111) oriented grains having the lowest surface energy and the share of ∑3 grain boundaries having the lowest interface energy increase from the start of crystallization to the end. This phenomenon could not be observed for the class G bricks, which show a decreasing ∑3 length fraction and a decreasing area fraction of {111} oriented grains. This energetically unfavourable grain structure development is not clear so far but it means another kind of energy minimization effect must exist within class G. This could be for instance the formation of dislocations. The grain structure investigations show clearly that especially the initially fine-grained struc-ture of the class F bricks, i.e. at the start of crystallization, influences beneficially the area fraction of recombination active defects and the solar cell efficiency subsequently. This ob-servation can be explained as follows. Reduced dislocation cluster formation: • The small grain sizes in combination with the low length fraction of ∑3 grain bounda-ries capture the dislocations within a grain. Dislocations are not able to move across the grain boundaries which have not the ∑3-type within moderate stress and tempera-ture fields. This prohibits the formation and expansion of large dislocation cluster. • The previously described energetically driven grain selection and the continuously in-creasing grain size from bottom to top leads to an overgrowth of grains. This means that also dislocated grains will disappear which also prohibits the formation of large dislocation cluster. Reduced possibility of dislocation formation: • Compared to the class G bricks the area fraction of {111} oriented grains is reduced. Therefore, the possibility of the formation of dislocations is reduced, because they would be activated first in {111} oriented grains taking the Schmidt factor in account which is lowest for {111} oriented grains. After the dislocation generation within a {111} oriented grain, the dislocation can move forward on 3 of 4 possible {111} slip planes which have an angle of 19.5° with regard to the growth direction. No other ori-entation has more slip planes for the dislocation movement which have an angle smaller 20° with regard to the growth direction. These arguments in combination with the high reproducibility of the characteristic initial class F structure can explain the observed low recombination active area fraction from start to end of crystallization which was smaller 5 % and especially the low variation of 2 % of the electrical active wafer area in between the class F bricks. One can also easily explain the higher recombination active area fraction up to 14 % and the large variation of 10 % between the class G bricks due to the obtained grain structure data. These differences in the recombination active area fractions are reflected in the solar cell efficiency which is 0.4 % higher for the class F bricks compared to the class G bricks. In consideration of the above mentioned reasons it is not beneficial for the industrial ingot production technology to increase the ingot height further, due to the fact that the advanta-geous initial grain structure properties of class F bricks disappear with increasing crystal height.

Este trabalho discute o efeito do tamanho de grão, frequência de excitação e resistividade elétrica nas perdas magnéticas, destacando-se a perda anômala. Também é proposto um método de sobreposição de histereses onde é revelada a região de ocorrência da perda anômala durante o ciclo de magnetização e desmagnetização, e posteriormente a curva de histerese da perda anômala é construída. Para tal, três ligas de aço de grão não orientado, com teor de silício de 2,05%, 2,45%, 3,3%, foram tratadas termicamente para aumento do tamanho de grão por crescimento. Cada liga foi tratada sobre a mesma sequência de temperatura, em recozimento contínuo. Os tamanhos de grão das amostras foram medidos pelo método de interceptos. A caracterização das propriedades magnéticas foi realizada por meio do quadro de Epstein. As amostras, no total de 21 conjuntos, foram ensaiadas em regime de frequência de 50, 60, 100, 150 e 200 Hz e regime quase estático (5mHz), ambos a 1 e 1,5 T. Possibilitando desta forma, a construção da histerese da perda histerética e total. Por meio dos resultados da perda total, histerética e parasita, a perda anômala pode ser calculada. Os resultados mostraram o comportamento da perda anômala (Pa) em função do tamanho de grão (l) do tipo Pa &#8733; l0,34 e em frequência (f) a relação de Pa &#8733; f1,65. A respeito do comportamento da perda anômala em função da resistividade elétrica (&#961;), os resultados encontrados são inconclusivos. Constatou-se empiricamente que, o tamanho de grão ótimo é função da frequência e da indução. A partir de tratamento matemático, a histerese da perda parasita mais histerética, foi construída e sobreposta à histerese da perda total. Os espaços vazios entre as curvas corresponder à perda anômala. É visto que a perda anômala ocorre em três regiões distintas da curva de histerese. Tais regiões podem supostamente ser associadas à fenômenos de dissipação de energia como; movimento de parede de domínio, nucleação de domínios e aniquilação de domínio. Como as histereses da perda total, histerética e parasita possuem a mesma indução, a histerese da perda anômala pode ser construída. O campo associado à perda anômala foi obtido como resultado da soma entre campo histerético mais parasita menos o campo magnético da perda total. / This paper discusses about the effect of grain size, excitation frequency and electrical resistivity in magnetic losses, especially the anomalous loss. Also is proposed a method of overlapping hysteresis where the region of occurrence of the anomalous loss during magnetization and demagnetization cycle is disclosed, and thereafter the hysteresis curve of anomalous loss is constructed. For this purpose, three non-oriented steel alloys, with silicon content of 2.05%, 2.45%, 3.3%, were heat treated to increase the grain size by grain growth. Each alloy was treated in the same sequence of temperature in continuous annealing. The grain sizes of the samples were measured by an intercept method. Characterization of magnetic properties was performed using the Epstein frame. The samples, in total 21 sets, were tested under a frequency of 50, 60, 100, 150 and 200 Hz and quasi-static regime (5mHz), both at 1 and 1.5 T. Thus allowing the construction of the hysteresis of quasi-static and total loss. Through the results of the total loss, quasi-static loss and parasite loss, the anomalous loss can be calculated. The results show the behavior of the anomalous loss (Pa) as a function of grain size (l) as Pa &#8733; l0.34 and frequency (f) the relationship of Pa &#8733; f1.65. Regarding the behavior of the anomalous loss due to resistivity (&#961;), the results are inconclusive. It was found empirically that the optimum grain size is a function of frequency and induction. From a mathematical treatment, the hysteresis of parasite loss plus quasi-static loss was constructed and overlapped to the hysteresis of total loss. The areas between the curves correspond to anomalous loss. It can be seen that anomalous loss occurs in three distinct regions of the hysteresis curve. Such regions may be associated with energy dissipation phenomena, such as: domain wall motion, nucleation and annihilation of domain. Since the hysteresis of total loss, quasi-static loss and parasite loss have the same induction, anomalous hysteresis loss can be constructed. The field associated with anomalous loss was obtained as a result of the sum of quasi-static field plus parasite field minus the magnetic field of the total loss.

Investigou-se o efeito do tamanho de grão austenítico na cinética e na morfologia do produto da reação bainítica de um ferro fundido nodular austemperado (FFNA). Foram estudados 3 tamanhos de grão austeníticos, a saber: GG (grão grosseiro), GM (grao mediano); e GR (grao refinado). A condição GR foi obtida pela austenitização rápida de microestruturas martensíticas. A condição GG foi obtida por tratamento de austenitização em duas etapas, de modo a, respectivamente, provocar o crescimento de grão e manter o teor de carbono igual aos das demais condições. Na segunda etapa do tratamento da condição GG ocorreu precipitação de grafita secundária, que acelerou significativamente a taxa de reação bainítica, possibilitando estudar o efeito da.variação na quantidade de interfaces austenita/grafita e austenita/ austenita sobre a cinética e a morfologia da reação bainítica. O refino do grão austenítico acelerou a cinética de reação, aumentou a proporção de ferrita alotriomorfa de contorno de grão, refinou a microestrutura bainítica (ferrita + austenita retida) e melhorou em 14% o limite de escoamento dos FFNA. Finalmente, a predominância de ferrira alotriomorfa na condição mais fina indica que a formação de interfaces incoerentes (mecanismo difusional ao inves de reação displaciva) durante a austenitização rápida da martensita (aquecimento de 100°C/ s). / The effect of austenite grain size on the kinetics and the morphology of the bainitic reaction in an austempered ductile iron (ADI) has been investigated, Three austenite grain sizes were produced: GG (coarse grain), GH (medium grain) and GR (fine grain), The GR condition was obtained by the rapid austenitization of martensitic microstructures The secondary graphite precipitation observed in GG condition strongly accelerated the rate of bainite formation and made possible the study of the effect of austenite/graphite interface on the kinetics of this reaction, The austenite grain refinement also accelerated the bainite precipitation, increased the proportion of grain boundary alotriomorphs ferrite, refined the bainitic microstructure and improved by 14% the yield stress of ADI, The predominance of grain boundary alotriomorphs in GR was associated to the structure of austenite/austenite interface formed during the rapid austenitization of the studied ductile iron at heating rates of 100oC/s. It is suggested that the dominant mechanism of austenitization in this condition is a thermally activated one (not a displacive transformation). The different morphologies of the austenite decomposition used the Duhê\'s morphological system.

Abstract Refining grain size is known to enhance mechanical properties also in austenitic stainless steels. To better understand the background of these properties, various reversion-treated structures were created in AISI 301LN (18Cr-7Ni-0.15N) steel and the microstructural features affecting flow behaviour and strength under monotonic and cyclic straining were investigated. Fully and partially reversed microstructures were produced using prior cold rolling thickness reductions in the range of 32–63% and both resistant and induction heating. Some selected reversed structures were also strengthening rolled to 20% reduction. The resultant microstructures were characterised using different research equipment and methods and their mechanical properties determined by microhardness, tensile and fatigue tests. The main interest was focused on the microstructural features of low-temperature reversed structures and the stability of austenite in them. Effective grain refinement was achieved after 56–63% rolling reduction. Depending on the reduction and annealing conditions, the reversed structures consisted of various amounts of submicron- and medium-sized austenite grains and retained phases. All the reversed structures showed non-homogenous, often bimodal grain size distribution. It was demonstrated that the stability of austenite was much reduced after annealing at temperatures &#8804; 850 &#176;C, which was attributed to precipitation occurring at these low temperatures. Fine grain size itself promoted higher stability, but the coarsest retained austenite was stable due to its special orientation. Therefore, medium-sized grains of 3–10 &#956;m, formed mainly from slightly deformed strain-induced martensite, appeared to be most unstable, the fraction being highest after the lowest reduction. The yield and fatigue strengths of the low-temperature reversion-treated structures were significantly higher than those of commercial 301LN. Fatigue strength corresponded to that of a 20% cold-rolled sheet. Strength was highly enhanced even after the lowest cold rolling reduction of 32%, for the lower strength of the coarser reversed grain structure was balanced by the higher fractions of strong retained austenite and martensite phases. / Tiivistelmä Austeniitin raekoon hienontamisen tiedetään parantavan merkittävästi ruostumattomien terästen mekaanisia ominaisuuksia. Hienorakeisten reversiorakenteiden muokkauslujittumiseen ja lujuuteen vaikuttavien tekijöiden yksityiskohtaista tutkimista varten tuotettiin AISI 301LN (18Cr-7Ni-0.15N) teräkseen 32–63% kylmävalssausreduktiota ja sen jälkeistä vastus- tai induktiokuumennusta käyttäen täysin sekä osittain reversoituneita mikrorakenteita. Lisäksi osa reversiorakenteista vielä lujitusvalssattiin 10–20% reduktioon saakka. Mikrorakenteiden karakterisointiin käytettiin monipuolisesti eri tutkimuslaitteita ja menetelmiä sekä mekaanisten ominaisuuksien määrittämiseen mikrokovuus-, veto- ja väsytyskokeita. Ensisijaisena tarkoituksena oli tutkia yksityiskohtaisesti matalassa reversiolämpötilassa muodostuneita mikrorakenteita sekä hienorakeisen austeniitin stabiilisuutta monotonisessa ja syklisessä kuormituksessa. Reversiokäsitellyissä rakenteissa esiintyi vaihteleva määrä hienoja (raekoko alle 1 &#956;m) ja keskisuuria (raekoko 3–10 &#956;m) austeniittirakeita mahdollisien karkeiden jäännösfaasien lisäksi kylmämuokkaustilasta ja lämpökäsittely-parametreista riippuen. Suuri muokkausaste edesauttoi selvästi raerakenteen hienontumista, mutta kaikki rakenteet olivat raekokojakaumaltaan epähomogeenisia. Työssä demonstroitiin kuinka alle 900 &#176;C:ssa hehkutetut reversiorakenteet ovat huomattavasti epästabiilimpia kuin korkeammassa syntyneet verrokkirakenteet, minkä osoitettiin johtuvan krominitridien erkautumisesta. Raekoon hienontuminen itsessään suosii suurempaa stabiilisuutta, mutta karkeimmat muokkautuneet jäännösausteniittirakeet olivat stabiileja niiden orientaation takia. Täten keskisuuret rakeet olivat epästabiileimpia. Keskisuurien rakeiden osoitettiin syntyvän pääasiassa vähän muokkaantuneesta martensiitista, ja niitä esiintyi eniten 32% reduktiolla valssatuissa rakenteissa. Matalassa lämpötilassa syntyneiden reversiorakenteiden lujuus oli merkittävästi korkeampi kuin kaupallisen teräksen. Väsymislujuus vastasi noin 20% lujitettuvalssattua tuotetta. Hehkutusta edeltänyt kylmämuokkausaste vaikutti vain vähän reversiorakenteiden lujuuteen, sillä vaikka pienin muokkausaste johti karkeimpaan keskimääräiseen raekokoon, siinä lujuutta lisäsivät kovat jäännösfaasit.

Ces travaux traitent de l’influence du procédé d’élaboration sur l’état métallurgique et les propriétés mécaniques et anti-corrosion des alliages de Ni-W nanostructurés, dans le but de mieux comprendre le rôle de différents paramètres physico-chimiques sur ces propriétés. Pour cela, deux techniques de dépôt sont utilisées : l’électrodéposition et la pulvérisation cathodique magnétron. Une approche multi-échelle associant différentes techniques permet la caractérisation fine de la morphologie, de la taille de grains, de la texture, de la nature des joints de grains ainsi que de la composition chimique des alliages et de leur contamination. En fonction de la technique d’élaboration utilisée, la relation entre la teneur en W et les paramètres métallurgiques est très différente avec un impact du W beaucoup plus marqué pour les électrodépôts par rapport aux alliages obtenus par pulvérisation. Les propriétés des revêtements sont évaluées par des tests de microdureté et des essais électrochimiques (courbe de polarisation et spectroscopie d’impédance électrochimique). Une augmentation de la microdureté est généralement observée avec la diminution de la taille de grains et l’augmentation de la teneur en W dans les alliages de Ni-W. Cependant, les valeurs de microdureté les plus importantes sont toujours atteintes pour de hautes teneurs en tungstène mais pas forcément pour les tailles de grains les plus faibles. Une limite dans l’augmentation de la microdureté avec la diminution de la taille de grains a donc été mise en avant. L’étude de la réactivité électrochimique des alliages en milieu acide a permis de montrer un rôle prépondérant du tungstène qui va dépendre du pH, du domaine étudié et des réactions associées. La morphologie de surface et les défauts structuraux vont également pouvoir influencer la réactivité des alliages de Ni-W avec une influence qui peut dépasser celle des solutés. En comparaison, les autres paramètres microstructuraux (taille et orientation des grains, nature des joints de grains et contamination) ne semblent avoir qu’un impact mineur sur le comportement électrochimique. / The aim of this study is to understand the influence of the deposition process on the metallurgical state and the mechanical and anti-corrosion properties of the nanostructured Ni-W alloys. Two processes are performed to obtain our alloys : the electrodeposition and the magnetron sputtering. A combination of several microstructural techniques at different scales has permitted the characterization of the morphology, the grain size, the crystallographic texture, the nature of grain boundaries and the concentrations of alloying elements. According to the elaboration process, the relationship between the W content and the metallurgical parameters is very different. A stronger influence of W is observed for the electrodeposited coatings by comparison with the alloys obtained by sputtering. The properties of the coatings are studied with microhardness measurements and electrochemical tests (polarization curve and electrochemical spectroscopy impedance). An increase of the microhardness is mainly observed with the decrease of grain size and the increase of tungsten content. But, the highest values of microhardness are always obtained for the highest tungsten content and not necessarily for the lowest grain size. So, a limit for the increase of microhardness with the decrease of grain size is put forward. The study of the electrochemical reactivity for the alloys in acidic media have shown a dominating role of the tungsten that depend on the pH, the studied domain and the reaction path associated with the corrosion process. The surface morphology and the structural defects have also an important influence on the reactivity of the Ni-W alloys that can exceed the impact of solute. As compared, the others metallurgical parameters (grain size, texture, grain boundaries and contamination) seem to have a minor influence on the electrochemical behavior.

O município de Viamão está localizado na região metropolitana de Porto Alegre, no estado do Rio Grande Sul. A barragem Mãe d\'Água foi construída em 1962, com o intuito de atender à demanda da Universidade Federal do Rio Grande do Sul, mais precisamente o Instituto de Pesquisas Hidráulicas, porém, devido à falta de planejamento urbano, durante os últimos quarenta anos, vem acarretando uma diversificada série de passivos ambientais, como contaminantes orgânicos e/ou inorgânicos. Neste seguimento, o presente trabalho busca avaliar as concentrações dos metais Zinco e Níquel, teores de matéria orgânica e a composição granulométrica nas diferentes profundidades amostradas em testemunhos de sedimentos produzidos nesta bacia hidrográfica que compõe a barragem Mãe d\'Água. As coletas de amostras foram realizadas em junho de 2014, sendo amostrados quatro testemunhos sedimentares distribuídos no lago da referida barragem. Para a extração dos testemunhos foi utilizado um amostrador de núcleo \"Piston Core\". Os sedimentos da fração menor que 63&#956;m foram destinados a análise química para verificação da presença e concentração dos elementos traço: Níquel (Ni) e Zinco (Zn). A metodologia de digestão ácida empregada é a EPA 3050, adotada pela U.S. Environment Protection Agency, sendo que as análises foram realizadas em duplicata e, para controle de qualidade, foram utilizados dois materiais de referência da USGS (U.S. Geological Survey): SGR-1b e SCO-1. Com os resultados obtidos, a caracterização granulométrica da sedimentação sob o barramento mostrou-se suscetível a contaminação por metais ao longo nas últimas décadas. Todas as amostras apresentaram concentrações de Zn e Ni acima do valor de background local e com padrões de crescimento, portanto, evidenciam a existência de enriquecimento dos sedimentos por estes elementos. Os teores de matéria orgânica quando correlacionados as concentrações de Zn e Ni evidenciaram o crescente enriquecimento nos testemunhos analisados, confirmando a alta afinidade destes elementos à sedimentos compostos de fração orgânica. O índice de geoacumulação para a maior parte das concentrações dos metais nas diferentes profundidades encontra-se caracterizadas como não poluída. Considerando que a área de estudo se caracteriza historicamente pela ocupação residencial, ações antropogênicas podem ser consideradas as principais provedoras dos passivos ambientais aos corpos d\'água. / The municipality of Viamão is located in the metropolitan region of Porto Alegre, state of Rio Grande do Sul. The Mãe D\'água Dam was built in 1962, so that demands from the Federal University of Rio Grande do Sul, more precisely the Institute of Hydraulic Research could be met. However, due to a lack of urban planning over the past forty years, the dam has caused several environmental liabilities, such as organic contaminants and / or inorganic contaminants. This manuscript addresses an evaluation of the concentrations of the metals zinc and nickel metals, organic matter content and particle size composition at different depths sampled in sediment cores produced in the watershed that comprises Mãe d\'Água. Four sediment core distributed in the dam lake were collected in June 2014, by \"Piston Core\" core sampler. Sediments whose fraction was lower than 63&#956;m were subjected to chemical analyses regarding the presence and concentration of nickel (Ni) and zinc (Zn). The acid digestion methodology employed was EPA 3050, adopted by the US Environment Protection Agency. The analyses were performed in duplicate and two USGS (US Geological Survey) reference materials, namely: SGR-1b and SCO-1 were used for the quality control. The particle size characterization of sedimentation under the bus has proved susceptible to metal contamination over the past decades. All samples showed concentrations of Zn and Ni higher than the local background values and growth patterns, which evidenced an enrichment of sediments. In comparison to the organic matter content, the Zn and Ni concentrations showed a growing enrichment, which confirmed the high affinity of these elements for sediments composed of organic fraction. The geoaccumulation index for most of the metal concentrations at different depths has been characterized as non polluted. As whereas the study area is historically by historically residential occupation, anthropogenic actions can be considered the main causes of environmental damage to water bodies.

L’objectif de ces travaux de thèse est d’étudier l’influence du rapport entre taille de défaut et longueur caractéristique de la microstructure, sur la limite de fatigue pour une durée de vie fixée d’un matériaux métallique,dans le cadre de la fatigue à grand nombre de cycle (FGNC). Le fer pur Armco est choisi comme matériau d’étude, car sa microstructure simple présente une seule longueur caractéristique à l’échelle mésoscopique (échelle des grains) : la taille de grain. Le but de l’étude revient ainsi à étudier la compétition entre un effet de structure (défaut surfacique)et un effet matériau (taille de grain) dans le cadre de sollicitations mécaniques en FGNC.Afin d’obtenir une taille de défaut comparable mais aussi inférieure à la taille de grain du matériau, un protocole thermomécanique a été élaboré pour augmenter la taille de grain. Des essais de FGNC, utilisant des éprouvettes issues des deux tailles de microstructures (matériau initial et celui écroui traité) dans lesquelles sont introduits des défauts hémisphériques de tailles différentes, ont été effectués pour estimer les limites de fatigue pour différents rapports taille de défaut / taille de grain. Lorsque les diagrammes de Kitagawa sont présentés en valeurs relatives(limite de fatigue / celle du matériau sans défaut en fonction de la taille de défaut / taille de grain), il existe une seule courbe qui combine les deux microstructures. Ce diagramme de Kitagawa sans dimension permet ainsi d’analyser la réduction de la limite de fatigue causée par un défaut. L’utilisation de la taille relative du défaut par rapport à la dimension microstructurale caractéristique apparaît comme plus pertinente que l’emploi de la taille physique réelle du défaut.Ces résultats expérimentaux sont utilisés pour reproduire les essais en FGNC avec des simulations Éléments Finis sur des microstructures 3D représentatives du fer Armco. La compétition existant entre la concentration de contrainte induite par le défaut géométrique et les régions fortement sollicitées de la microstructure engendrées parl’anisotropie du comportement mécanique des grains est étudiée. Un critère mésoscopique (à partir des grandeurs mécaniques moyennées par grain) basé sur une approche statistique permet de retrouver l’allure du diagramme de Kitagawa adimensionné, c’est-à-dire la taille relative du défaut critique à partir de laquelle ce dernier prend le passur l’hétérogénéité de la réponse de la microstructure et conditionne ainsi la tenue en fatigue du polycristal. La modification du critère mésoscopique par la prise en compte des hétérogénéités intragranulaires (via l’écart-type par grain des grandeurs mécaniques) est discutée. / The objective of this thesis is to study the influence of the ratio between the defect size and themicrostructure characteristic length on the fatigue limit (for a fixed fatigue life) of a metallic material, under highcycle fatigue (HCF). Pure Armco iron is chosen because its simple microstructure has a single characteristic lengthat the mesoscopic scale (grain scale) : the grain size. The aim of the study is thus to study the competition betweena structural effect (surface defect) and a material effect (grain size) in the context of mechanical stresses in HCF.In order to obtain a comparable different grain size, a thermomechanical protocol has been developed. HCF tests,using specimens from both microstructure sizes (initial material and processed hardened material) in which hemisphericaldefects of different sizes were introduced, were performed to estimate the fatigue limits for different defectsize / grain size ratios. When Kitagawa diagrams are presented in relative values (fatigue limit / fatigue limit ofdefect free material versus defect size / grain size), there is a single curve that combines the two microstructures.This dimensionless Kitagawa diagram thus makes it possible to analyze the reduction of the fatigue limit inducedby a defect. The use of the relative size of the defect with respect to the characteristic microstructural dimensionappears to be more relevant than the use of the physical size of the defect.These experimental results are used to reproduce the HCF tests with Finite Element simulations on 3D microstructuresrepresentative of Armco iron. The competition existing between the stress concentration induced by thegeometrical defect and the highly stressed regions of the microstructure generated by the anisotropy of the mechanicalbehavior of the grains is studied. A mesoscopic criterion (involving mechanical quantities averaged by grain)based on a statistical approach allows to find the evolution of the dimensionless Kitagawa diagram, ie the relativesize of the critical defect from which it predominates over the response heterogeneity of the microstructure and thusgoverns the fatigue behavior of the polycrystal. The modification of the mesoscopic criterion by taking into accountintragranular heterogeneities (with the standard deviation per grain of mechanical quantities) is discussed.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Ionic transport in metal oxides is crucial for the functioning of a broad range of different components, such as heat resistant alloys designed for high temperature applications and oxide electrolytes in solid oxide fuel cells. This thesis presents results from in situ electrochemical studies of properties related to ionic transport in metal oxides that are important for their applications as protective oxides and ionic conductors. Heat resistant alloys of alumina-former type are known to form an adherent, slowly growing and protective aluminium oxide (Al2O3) scale that protects metals from chemical degradation at high temperature. In situ impedance spectroscopy was used to study highly pure and dense samples of a-alumina in the temperature range 400 – 1000 °C. It was shown that surface conduction on the sample could severely distort the measurement below 700 °C. The magnitude of the distortions appeared to be sensitive to the type of electrodes used. The use of a so-called guard electrode was shown to effectively block the surface conduction in the measurements. By varying the grain size of the sintered alpha-alumina samples, the influence of grain size on the overall conductivity of the a-alumina was studied. It was shown that the activation energy for conductivity increased as the grain size decreased. Molecular dynamics calculations were performed in order to elucidate whether Al- or O ions are dominant in the ionic conductivity of the alpha-alumina. Comparing the calculation and experimental results, the dominating charge carrier was suggested to be oxygen ions. Moreover, the ionic transport in thermally grown alumina-like oxide scales formed on a FeCrAl alloy was studied in situ by impedance spectroscopy between 600 and 1000 °C. It was shown that the properties of these scales differ largely from those of pure and dense alpha-alumina. Furthermore, the conductivity is mainly electronic, due to the multiphase/multilayer microstructure and substantial incorporation of species from the base metal. However, the diffusivity obtained from the ionic conductivity was in line with diffusion data in literature obtained by other methods such as thermogravimetry. Besides, the initial stage of oxidation of a number of Fe-, Ni- and Co-based alloys at temperatures between 500 and 800 °C was studied in situ by high temperature cyclic voltammetry, in which the oxygen activity was changed over a wide range. From the resulting voltammograms the redox reactions occurring on the alloy surface could be identified. It was concluded that the base metal oxidized readily on these alloys before a protective chromia- or alumina-like scale is formed. The base metal oxide is most likely incorporated into the more protective oxide. Further, the oxygen ionic conductivity of highly pure and fully dense yttria-stabilized zirconia produced by spark plasma sintering was studied by impedance spectroscopy. The aim was to evaluate intrinsic blocking effects on the ionic conduction associated with the space charge layer in the grain boundary region. It was observed that the ionic conductivity of the spark plasma sintered oxides is equal or slightly higher than what has been achieved by conventional sintering methods. In addition, it was shown that the specific grain boundary conductivity increases with decreasing grain size, which can be explained by a decreasing Schottky barrier height (i.e., decreasing blocking effect). The quantitative results from this work verify the space charge model describing the influence of grain size on the ionic conductivity of yttria-stabilized zirconia through dopant segregation and oxygen vacancy depletion along the grain boundaries. / QC 20100825

Fosforutsläpp kan leda till övergödning i vattenrecipienten om kritiska nivåer överskrids. De enskilda avloppen står idag för en relativt stor andel av Sveriges fosforutsläpp jämfört med de kommunala avloppen. Detta kan sättas i bakgrund av att staten, alltsedan 1970-talet, har lagt ner stora resurser på att reducera utsläppen hos kommunala avlopp, medan en motsvarande satsning på de enskilda avloppen uteblivit. Merparten av dagens enskilda avlopp utgörs av markbaserade reningssystem, det vill säga avloppslösningar där avloppsvattnet får passera genom markmaterial för att renas. Fosforreningen i markbaserade reningssystem har forskningshistoriskt sett inte varit en prioriterad fråga, vilket har lett till kunskapsbrist inom området. Naturvårdsverket har i och med miljöbalkens införande skärpt sina krav på fosforreningen hos enskilda avlopp. Trots att Naturvårdsverket nu har satt upp exakta kravgränser på fosforutsläpp, exempelvis att en normal skyddsnivå motsvarar en rening på 70 %, saknas dock råd för hur gemene man, inför byggandet av ett markbaserat reningssystem, ska kunna uppskatta fosforreningsförmågan i markmaterialet. Emellertid rekommenderar Naturvårdsverket att man inför byggandet ska uppskatta markmaterialets hydrauliska konduktivitet, en uppskattning som ofta utförs genom att mäta markmaterialets kornstorleksfördelning. Det finns även forskning som tyder på att kornstorleksfördelningen skulle kunna ha samband med fosforreningen. Syftet med detta examensarbete var framförallt att utvärdera om kornstorleks- fördelningen kan användas som ett mått på fosforreningen. Som ett sidospår till detta utvärderades även om den hydrauliska konduktiviteten kan bestämmas ur kornstorleks- fördelningen. Empiriska formler har vid tidigare studier etablerats för detta, men frågan är om dylika empiriska formler gäller för de undersökta markbaserade reningssystemen. Undersökningens resultat tydde på ett samband mellan kornstorlek och hydraulisk konduktivitet medan det inte kunde påvisas något samband mellan kornstorleks- fördelning och fosforrening. Det är därmed önskvärt att finna ett annat mått på fosforreningen i markbaserade reningssystem. Kan vi inte uppskatta hur mycket de markbaserade reningssystemen bidrar till övergödningen kan vi inte heller väga denna negativa miljöpåverkan mot de markbaserade systemens fördelar, såsom relativt låg energiförbrukning och relativt små utsläpp av växthusgaser. / Release of phosphorus is one of the contributing factors of eutrophication in aquatic recipients. In Sweden, on-site wastewater treatment represents large emissions of phosphorous per person in comparison to municipal wastewater treatment. This can be put in the context of the Government’s large investments for reducing phosphorus in municipal wastewater treatment plants, while no corresponding investment has yet been made in the field of on-site wastewater treatment. In Sweden, the on-site wastewater treatment systems of today mainly consist of WSAS (Wastewater soil absorption systems), i.e. systems where wastewater is cleaned by passing though soil material. During the history of research about WSAS issues of phosphorous removal have not been first priority, which has led to a considerable lack of knowledge regarding these issues. Since 1999, when the Swedish regulations of environmental law were established, the SEPA (Swedish Environmental Protection Agency) has tightened up their demands of phosphorus removal in on-site wastewater treatment systems, for instance by stating that a phosphorous removal of 70% shall be reached to accomplish a “normal level of protection”. Despite this fact, there are no recommendations of how to estimate phosphorus removal in the soil material. However, the SEPA recommends estimation of hydraulic conductivity before building WSAS. This estimation is usually made by measuring grain size distribution in the soil material. One interesting fact is that there, according to some scientists, might be a connection between grain size distribution and phosphorus removal. The aim of this thesis was mainly to investigate if measure of grain size distribution can be used in order to estimate phosphorus removal. The aim was also to evaluate if grain size distribution is a good indicator of hydraulic conductivity in the investigated WSAS. It was concluded that grain size distribution is a suitable indicator of hydraulic conductivity, but not a suitable indicator of phosphorus removal. Thus, we still need to find an easy way to estimate the phosphorus removal in WSAS. If we do not know the extent of impact on eutrophication by WSAS, we cannot weigh this negative impact against the positive aspects of relatively low energy usage and low release of green house gases compared to other on-site wastewater treatment systems.