The primary objective was to predict the relative storage capacity of carbonate rocks relevant for carbon dioxide sequestration. To achieve this, a detailed pore scale characterization of model carbonate rocks, Indiana Limestone and Pink Dolomite, was conducted utilizing micro-computed tomography (microCT) data using pore network modeling and invasion percolation simulations. For the first time in literature, Pink Dolomite’s pore space characteristics were analyzed. A secondary objective was to compare thresholding techniques as applied to carbonates which exhibit dual porosity (porosity at multiple length scales). The analysis showed the sensitivity of existing methods to the thresholding technique, imaging method and material. Overall, the contributions of this work provide an assessment of two carbonates relevant for carbon capture and storage at the pore scale; and a preliminary assessment into thresholding dual porosity carbonates.

Sphaerodoridae is a group of benthic marine worms (Annelida) characterized by the presence of spherical tubercles covering their whole surface. They are commonly considered as belonging to Phyllodocida although sistergroup relationships are still far from being understood. Primary homology assessments of their morphological features are lacking, hindering the appraisal of evolutionary relationships between taxa. Therefore, our detailed morphological investigation focuses on different Sphaerodoridae as well as on other members of Phyllodocida using an integrative approach combining scanning electron microscopy (SEM) as well as immunohistochemistry with standard neuronal (anti-5-HT) and muscular (phalloidin-rhodamine) markers and subsequent CLSM analysis of whole mounts and sections. Furthermore, we provide histological (HES) and light microscopical data to shed light on the structures and hypothetical function of sphaerodorid key morphological features. We provide fundamental details into the sphaerodorid morphology supporting a Phyllodocida ancestry of these enigmatic worms. However, the muscular arrangement and the presence of an axial muscular pharynx is similar to conditions observed in other members of the Errantia too. Furthermore, nervous system and muscle staining as well as SEM and histological observations of different types of tubercles indicate a homology of the so called microtubercles, present in the long-bodied sphaerodorids, to the dorsal cirri of other Errantia. The macrotubercles seem to represent a sphaerodorid autapomorphy based on our investigations. Therefore, our results allow comparisons concerning morphological patterns between Sphaerodoridae and other Phyllodocida and constitute a starting point for further comparative investigations to reveal the evolution of the remarkable Sphaerodoridae.

Poröse Polymermembranen spielen in der Industrie und Forschung als Filtrationsmedien eine bedeutende Rolle. Eine besondere Form dieser Membranen sind die sogenannten Mikrosiebe, die sich im Vergleich zu herkömmlichen Filtermedien durch eine Membrandicke kleiner als der Durchmesser der Poren, eine enge Porengrößenverteilung und eine hohe Porendichte auszeichnen. Dies führt zu einer hohen Selektivität und Permeabilität dieser Mikrosiebe. Aufgrund der geringen Membrandicke sind sie jedoch, beispielsweise beim Einsatz als Filtermedien, sehr empfindlich gegenüber mechanischer Belastung und benötigen üblicherweise eine zusätzliche (externe) Stützstruktur. Die vorliegende Arbeit beschäftigt sich mit der Herstellung mikrosiebartiger Polymermembranen, bei denen die Darstellung der späteren Trennschicht und Stützstruktur in einem Prozess erfolgt – den hierarchisch strukturierten porösen Membranen. Es werden zwei neue Verfahren zur Darstellung dieser Membranen vorgestellt. Im ersten Verfahren wird das Prinzip der partikel-assistierten Benetzung mit den sogenannten Kondensationsmustern (Breath Figures Patterns), im zweiten Verfahren mit der Tintenstrahltechnik kombiniert. In beiden Fällen enthalten die resultierenden Polymermembranen die gewünschte hierarchische Porenstruktur, d. h. sie weisen eine Trennschicht mit submikrometergroßen Poren auf der einen Seite und eine Stützstruktur mit größeren, mikrometergroßen Poren auf der anderen Seite auf. Um die Membranen, welche durch Kombination der partikel-assistierten Benetzung mit den Kon-densationsmustern hergestellt werden, für einen möglichen Einsatz als Filtrationsmedium zu charakterisieren, werden Untersuchungen bezüglich des Permeatflusses und der Permeabilität sowie zum Rückhaltevermögen durchgeführt.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / During the history of the Civil Engineering, it is witnessed the appearance of a new age, which emphasizes quality in general, and durability, in particular, of the concrete structures. As a result of a continuable search for quality, an evolution in a relatively new field is observed, named Structural Pathology, which relates to the study of structural imperfections in constructions. An efficient solution for this problem is the structural repair, that appears as a strong market share of the industry of the civil construction, motivating the development of a number of materials and procedures of repair that aim to reestablish the original conditions of the damaged structure in order to extend its service life. For the protection and the restoration of the concrete structures, there were developed repair materials destined to different situations of application. The Microscopy, historically applied to the biomedical sciences, field has been spreaded out to the science of the materials field as well, becoming an important tool in the study of diverse properties. The main objective of this research is to investigate the form of linking and bond between repair mortars and concrete, by using microscopy. In this research 247 micrographs were analysed from 24 samples of four types of repair mostars amongst the ones found in the market had been analyzed. The typical morphologic characteristics of those materials were studied through of the optic microscope (OM) and the scanning electron microscope (SEM). The results presented in research provides the understanding of the microscopical analisis related to the bond of someone repair materials. / Ao longo da história da Engenharia Civil, testemunha-se o surgimento de uma nova era, na qual se enfatiza a qualidade em geral e, particularmente, a durabilidade das estruturas de concreto. Como resultado de uma incessante busca pela qualidade, observa-se uma evolução em um campo relativamente novo, designado por Patologia Estrutural, que se relaciona ao estudo de falhas estruturais em obras civis. Uma solução eficaz para este problema é a recuperação estrutural, que surge como um forte segmento de mercado da indústria da construção civil, motivando o desenvolvimento de uma série de materiais e procedimentos de recuperação que visam a restabelecer as condições originais da estrutura danificada e ampliar a sua vida útil. Para a proteção e recuperação das estruturas de concreto, foram desenvolvidos materiais específicos destinados a diferentes situações de aplicação. A microscopia, historicamente aplicada no seguimento das ciências biomédicas, tem sido difundida também para a ciência dos materiais, tornando-se uma ferramenta importante no estudo de diversas propriedades. O objetivo principal deste trabalho é investigar a forma de ligação e aderência entre o concreto e o material de reparo, mediante microscopia. Nesta pesquisa, foram analisadas 247 micrografias em 24 amostras de quatro tipos de argamassas de reparo dentre os encontrados no mercado. As características morfológicas típicas destes materiais foram estudadas com o auxílio do microscópio óptico (MO) e do microscópio eletrônico de varredura (MEV). Os resultados apresentados neste trabalho auxiliam a compreensão da análise microscópica relacionada à aderência de um determinado material de reparo ultilizado. / Mestre em Engenharia Civil

O estudo da ontogênese floral é essencial para uma melhor compreensão dos processos evolutivos envolvidos no desenvolvimento dos órgãos reprodutivos dos vegetais. Este trabalho teve por objetivo analisar a ontogênese floral das espécies C. echinata, C. peltophoroides e C. ferrea, da família Fabaceae/ Caesalpinioideae Foram realizados estudos morfo-anatômicos com o emprego de técnicas de microscopia eletrônica de varredura e microscopia óptica. Os resultados obtidos permitiram determinar que a ontogênese floral das três espécies são similares: o meristema da inflorescência é indeterminado e inicia a formação de brácteas acropetalarmente. Cada bráctea protege um único meristema floral. O primórdio da sépala abaxial é o primeiro a ser formado pelo meristema floral, seguido dos primórdios das sépalas laterais e adaxiais, de forma unidirecional. Os primórdios das pétalas e dos estames epissépalos e epipétalos são iniciados a seguir. A formação do carpelo inicia-se com a formação de uma protuberância no centro do meristema floral e quando o primórdio do carpelo atinge cerca de 100 µm de altura, o mesmo inicia uma invaginação em seu lado adaxial formando uma fenda cuja superfície interna originará a placenta. Nos estágios que precedem a antese, há a diferenciação de células papilares no estigma. Os resultados obtidos neste trabalho de descrição da ontogênese floral em Caesalpinia poderão servir de fundamentação para futuros estudos dos aspectos moleculares do desenvolvimento reprodutivo em leguminosas. / The study of the floral ontogeny is essential for the understanding the evolutionary processes involved in the development of the floral organs. The aim of this work was to analyse the floral ontogeny the species C. echinata, C. peltophoroides and C. ferrea, from the family Fabaceae/ Caesalpinioideae. Scanning electron microscopy and light microscopy techniques were used. The observed results indicated that the ontogeny events of the tree species were similar: the inflorescence apical meristem is indeterminate and initiates bracts in an acropetal order. Each bract protects a single floral meristem. The first floral organ formed is the abaxial sepal and it is followed by the lateral and adaxial sepal primordia in a unidirecional order. The whorls of petal and antepetalous and antesepalous stamen primordial are the next to begin. The carpel primordium arise as a mound in the center of the floral meristem. When the carpel primordium is about 100µm high, a cleft is formed in its adaxial side, on the site where the placenta will be formed. At anthesis, the stigma differentiates papilate cells. The results obtained with this descriptive work will serve as a foundation for future studies of the molecular aspects of reproductive development of legumes.

Cette recherche vise à analyser et à identifier, par des essais, le comportement au fluage d'une argile de type kaolinite sous un état de contraintes triaxial. Une investigation fine de l’état microstructural, avant et après fluage, a par ailleurs été réalisée. Les résultats macroscopiques ont permis de constater que des phénomènes de dilatance et de contractante s’amplifient pendant le fluage. Les résultats montrent également que la position, sur le plan des contraintes (p'-q), du niveau de contrainte vis-à-vis des différents domaines volumétriques, contrôle le développement de la déformation au fluage et du taux de déformation. Les résultats de MEB ont montré que l'évolution microstructurale de l'argile, après le chargement mécanique, dépend fortement de l'histoire du chargement. / The objective of this research is to analyze the creep behavior of a typical clay along triaxial tests, moreover, to analyze the microstructural mechanisms of creep. Analysis on the macroscopic results ascertained that both dilatancy and contractancy phenomena could occur during creep. The magnitude of the dilatancy/contractancy during creep was guided by the test conditions: stress level and the over consolidation ratio, which specifically governed the direction of the volumetric strain variations. The results of SEM indicated that the microstructural evolution of the clay after the mechanical loading depend on the stress history. Afterwards, the structural evolution in creep phase depends on the structural pattern developed in monotonic loading

[pt] Este trabalho teve por objetivo avaliar a morfologia de biofilmes, formados em superfície de aço API 5L X80 submetida a um fluido com baixo BSW (Basic Sediment Water), ou seja, baixo teor de água em óleo, através de análise por Microscopia Eletrônica de Varredura (MEV), determinar a cinética e quantificar os grupos bacterianos de formação destes biofilmes, e avaliar a biocorrosão causada por estes microrganismos. Foram realizadas alterações no protocolo original de preparo de amostras, com a finalidade de obter melhor definição das morfologias avaliadas. Realizaram-se estudos dinâmicos (looping) e em condições estáticas, com e sem a adição de agente biocida. Utilizando-se como fluido de processo o óleo coletado no terminal da Petrobras em Barra do Furado que tem como característica um BSW de aproximadamente 1 por cento de água. Para alcançar os objetivos descritos foram quantificadas bactérias sésseis (bactérias facultativas heterotróficas, bactérias precipitantes do ferro, bactérias anaeróbias heterotróficas e bactérias redutoras de sulfato) através da técnica do número mais provável (NMP). A intensidade do processo corrosivo foi avaliada através da análise dos pites formados nos cupons por microscopia óptica. A seqüência de fixação com alteração do protocolo inicial, permitiu uma melhor preservação estrutural do biofilme obtendo-se assim imagens com melhor resolução, tendo em vista que a fixação primária com glutaraldeído fixa principalmente proteínas pelo estabelecimento de ligações divalentes com grupamento amino, e a pós-fixação em tetróxido de ósmio reage com os lipídios. Quanto a cinética, observou-se também que na presença de fluido oleoso, a formação do biofilme só é detectada após 15 dias de exposição. A adição do agente biocida inibiu o crescimento do biofilme, não sendo detectada a presença de células cultiváveis após 7 dias em contato com o fluido contendo o agente químico. / [en] This study aims to evaluate the morphology of biofilms formed on the surface of API 5L X80 steel exposed to a low BSW (Basic Sediment Water) fluid comprising oil of a low water content. The analisys was performed using scanning electron microscopy (SEM) in order to determine the formation kinetics, to quantify and identify the bacterial groups present as the film formed, and to evaluate the biocorrosion caused by these organisms. Modifications were made to the original sample preparation protocol, in order to better define the film morphologies. Studies were undertaken applying either static or dynamic (looping) conditions, bith with and without the addition of biocides. The process fluid used was oil collected from the Petrobras Barra do Furado Terminal, characterized by its 1 percent BSW. The evaluation was performed quantifying the sessile bacteria present in the film (heterotrophic bacteria, iron bacteria, anaerobic bacteria e sulphate reducing bacteria) via the Most Probable Number (MPN) technique. The intensity of the corrosion process was determined by the analysis of pits forme in the testpieces, by optical microscopy. The application of a sample fixation sequence, in addition to modifications of the inicial sample preparation protocol, permitted the improved preservation of the biofilm structures, thereby permitting higher resolution images. The primary fixing agent, containing gluteraldehyde, principally fixes proteins, by establishing divalent bonds with amino groups, while the post-fixation stage with osmium tetroxide invloves reactions with lipid groups.With regard to the film deposition kinetics, it was observed that biofilm formation could only be detected after 15 day s exposure to the oily fluid. The addition of a biocide, inhibited the growth of the film, no cultivatable cells being present after 7 days contact with the treated fluid.

This project relates to the non-classical growth of inorganic crystals with interesting morphologies that are highly desirable in industry. All crystals were synthesized via hydrothermal or solvothermal methods and their growth was studied by stopping each reaction at a range of different times, extracting the particles and analysing them using a variety of characterisation techniques. The main techniques used were scanning electron microscopy and transmission electron microscopy but other techniques, such as powder X-ray diffraction and thermal gravimetric analysis, were also employed. Decorated ZnO microstadiums were studied where ZnO nanocones coat the inner and outer columnar walls of ZnO microstadiums. It was revealed that the polymer in the synthetic solution enhanced the aggregation of nanocrystallites of precursor ions on the microstadium surfaces, which then underwent recrystallization, forming ZnO nanocones. The presence of organic agents was also found to be crucial in the non-classical growth mechanisms of CaCO₃ and RHO-ZIF crystals as the presence of charged groups on the organic molecules led to the aggregation of precursor molecules/ions, preventing classical growth. The disordered aggregates underwent surface recrystallization, forming ‘core-shell' structures where a thin layer of single crystal encased a disordered core. Over time the crystallisation extended from the surface inwards, towards the core, until true single crystals were formed. Organic molecules were also shown to play a role in the non-classical growth of 8-branched Cu₂O structures. In this case, however, studies of the electronic configuration of the main terminating facets of Cu₂O crystals revealed another key factor in their non-classical growth. Terminating hydroxyl groups on the Cu₂O surfaces could have different charges depending on the number of Cu⁺ ions they were coordinated to. The terminating {111} faces were the only ones to be coated with negatively charged hydroxyl groups, which explained the rapid growth on these surfaces as they were able to attract the positively charged metal/polymer precursor clusters. This new phenomenon was also found to be the main driving force in the rapid growth of branches in snowflake-like Fe₂O₃ crystals despite no organic agent being used. In this case, the {11-20} faces of the seed crystals had positively charged hydroxyl groups that were able to rapidly attract the negatively charged [Fe(CN) ₆]³⁻ ions in the aqueous solution.

Magister Scientiae - MSc / The toxicity of microcystin is associated with the inhibition of serine/threonine protein phosphatases 1 and 2A, which can lead to hepatocyte necrosis and haemorrhage. Analysis of microcystin is most commonly carried out using reversed-phase high performance liquid chromatographic methods (HPLC) combined with ultra-violet (UV) detection .The ability of these techniques to identify unknown microcystin in environmental samples is also restricted by the lack of standard reference materials for the toxins. Highly specific recognition molecules such as antibodies and molecularly imprinted polymers (MIPs) have been employed in the pre-concentration of trace levels of microcystin from water and show great potential for the clean-up of complex samples for subsequent analysis. New biosensor technologies are also becoming available, with sufficient sensitivity and specificity to enable rapid ‗on-site‘ screening without the need for sample processing. In this work we constructed a Protein phosphatase biosensor for detection of microcystin-LR in aqueous medium, onto polyamic acid/graphene oxide (PAA: GO) composite electrochemically synthesised in our laboratory. The composites were synthesised at three different ratios i.e. 50:50, 80:20 and 20:80 to evaluate the effect of each component in the search to produce highly conductive mediator platforms. The electrochemistries of the three different composites were evaluated using CV and SWV to study interfacial kinetics of the materials as thin films at the glassy carbon electrode. The phosphatase biosensor parameters were evaluated using CV, SWV, EIS and Uv-vis spectroscopy. The affinity binding of the microcystin-LR to protein phosphatase 2A was investigated using electrochemical impedance spectroscopy which is a highly sensitive method for measuring interfacial kinetics of biosensor systems.

Lithium represents one of the strategic elements for the rest of the 21st century due to its increasing demand in technological applications. Therefore, new efforts should be focused on the optimization of mineral characterization processes, which link the ore properties with its behaviour during downstream processes. These efforts should result in reducing operational risks and increasing resources utilization. The methodology presented in this study is based on the application of several classification techniques, aiming the mineral and textural characterization of two spodumene pegmatite deposits within the Keliber Lithium Project. Twelve textural classes have been proposed for the textual classification of the ore, which have been defined through the recognition of the main mineral features at macro- and micro-scale. The textural classification was performed through the application of drill core logging and scanning electron microscopy. Six classes are proposed to describe the characteristics of the spodumene ore. Six additional classes describe the main properties of the rocks surrounding the ore zone. Image analysis was implemented for the generation of mineral maps and the subsequent quantification of spodumene and Li2O within the analysed drill core images. The image segmentation process was executed in Fiji-ImageJ and is based on eight mineral classes and a set of seven feature extraction procedures. Thus, quantification of spodumene and Li2O is estimated by textural class. Hyperspectral images were used as a reference for assessing the estimations made through images analysis. A machine learning model in Weka allowed forecasting the behaviour of the twelve textural classes during spodumene flotation. This model is fed by metallurgical data from previous flotation tests and uses Random Forest classifier. The proposed methodology serves as an inexpensive but powerful approach for the complete textural characterization of the ore at Keliber Lithium Project. It provides information about: (1) mineral features at different scales, (2) spatial distribution of textures within the pegmatite body, (3) quantification of spodumene and Li2O within the drill cores and (4) processing response of each textural class. However, its application requires wide knowledge and expertise in the mineralogy of the studied deposits. / <p>Thesis Presentation.</p><p>Textural and Mineralogical Characterization of Li-pegmatite Deposit: Using Microanalytical and Image Analysis to Link Micro and Macro Properties of Spodumene in Drill Cores.  Keliber Lithium Project, Finland.</p><p></p>