Química mineral do vulcano-plutonismo paleoproterozoico da região de São Félix do Xingu (PA), Cráton Amazônico

As formações Sobreiro e Santa Rosa são resultado de intensas atividades vulcânicas paleoproterozoicas na região de São Félix do Xingu (PA), SE do Cráton Amazônico. A Formação Sobreiro é composta por rochas de fácies de fluxo de lava andesítica, com dacito e riodacito subordinados, além de rochas que compõem a fácies vulcanoclástica, caracterizadas por tufo, lapilli-tufo e brecha polimítica maciça. Essas rochas exibem fenocristais de clinopiroxênio, anfibólio e plagioclásio em uma matriz microlítica ou traquítica. O clinopiroxênio é classificado predominantemente como augita, com diopsídio subordinado, e apresenta caracterísiticas geoquímicas de minerais gerados em rochas de arco magmático. O anfibólio, representado pela magnesiohastingsita, foi formado sob condições oxidantes e apresenta texturas de desequilíbrio, como bordas de oxidação vinculadas à degaseificação por alívio de pressão. As rochas da Formação Santa Rosa foram extravasadas em grandes fissuras crustais de direção NE-SW, têm características de evolução polifásica e compõem uma fácies de fluxo de lava riolítica e riodacítica e uma fácies vulcanoclástica de ignimbritos, lapilli-tufos, tufos de cristais félsicos e brechas polimíticas maciças. Diques métricos e stocks de pórfiros graníticos e granitoides equigranulares completam essa suíte. Fenocristais de feldspato potássico, plagioclásio e quartzo dispersos em matriz de quartzo e feldspato potássico intercrescidos ocorrem nessas rochas. Por meio de análises químicas pontuais dos fenocristais em microssonda eletrônica, foram estimadas as condições de pressão e temperatura de sua formação, sendo que o clinopiroxênio das rochas intermediárias da Formação Sobreiro indica profundidade de formação variável entre 58 e 17,5 km (17,5 - 4,5 kbar), a temperaturas entre 1.294 e 1.082 ºC, enquanto o anfibólio cristalizou-se entre 28 e 15 km (7,8 - 4,1 kbar), o que sugere uma evolução polibárica. Assim, propõe-se um modelo de geração de magma basáltico hidratado com base na fusão parcial de cunha mantélica e no acúmulo na crosta inferior em uma zona quente, a partir da qual os magmas andesíticos e dacíticos são formados pela assimilação de crosta continental e cristalização fracionada.

ECOLOGICAL MODELING OF TALITROIDES TOPITOTUM (CRUSTACEA: AMPHIPODA)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo de falhas por fadiga em caldeiras

In recent years, increasing demand for energy has led to studies to increase the amount of electricity produced. Due to this fact, more and more boilers are becoming important sources of electricity generation. To raise the efficiency of energy generated in the boilers is necessary to raise the steam pressure and temperature to values previously unimaginable. The use of more resistant materials and maintenance practices and most appropriate operation made it possible. The objective of this study is to test the main types of failure in a chemical recovery boiler, in particular due to fatigue in the superheater, because it is a component subjected to high temperatures and thus more subject to different failures. In this manner this study aims to reduce the incidence of unscheduled maintenance shutdowns, increasing the operation time under appropriate conditions. Modeling performed in this study, the failure did not occur, because we considered only the mechanical stress. Under normal conditions, mechanical stress in combination with thermal stresses can cause cracks in the tubes due to cyclical stresses, leading to fatigue failure

Estudo das alterações das propriedades mecânicas em aço A-516 grau 70 soldado e submetido a tratamento térmico de alívio de tensões

Pressure vessels are equipments that require a great care because of their high cost and human life risk in case of fail, and its fabrication methods are different for each manufacturer. Normally, pressure vessels and its parts are fabricated by welding, which may change local properties of metals. The head of a pressure vessel is a very important structural component and it is fabricated by welding and mechanical conformation. Because its excellent mechanical properties, de steel A-516 Grade 70 is often used in manufacturing of large pressure vessels that are subjected to high pressure and temperature, but was verified that its mechanical resistance is decreased when submitted to a tension relief heat treatment. By experience it was defined that before mechanical conformation of the head of a large pressure vessel, the steel should be submitted to a stress relief heat treatment in order to facilitate the mechanical conformation, but there is no quantitative analysis to prove this method and study its possible risks. In the present work the steel A-516 Grade 70 demonstrated a decrease of its mechanical resistance when submitted to a stress relief heat treatment, but keeping above the minimum limit defined in the literature. By other side its ductility was substantially increased, being possible to deduce that the stress relief heat treatment before mechanical conformation is a viable e recommended technique, but with reservations. With the data acquired during the fabrication e preparation of the specimen and the result of the tests, it was possible to elaborate a welding procedure that provides the same results obtained in this present work

Construção e avaliação térmica de um sistema concentrador parabólico com seguidor solar

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dispositivo de microdescargas em gases na pressão atmosférica

This work describes the development of an electro-mechanical micro-discharges device operating at ambient condition of pressure and temperature, capable to produce plasma jets for surface finishing. The discharges are produced through a needle shape electrode hollow cathode type by which flows the helium gas. The voltage applied on the electrode is provided for an AC/AC switching voltage converter of full-bridge topology. The converter is energized by a power line of 110/220 VAC, 60 Hz and gives a 1000 V peak-to-peak from 5 kHz to 40 kHz square waveform output. The output frequency is defined by a control signal provided by an external signal generator. The equipment setup includes output acquisition of voltage and current and a photo-detector for photo-electrical measurements, which allows an optical characterization of the plasma jet

Projeto de adaptação do sistema de injeção do túnel transônico para ensaios em bocais de foguete

In this work, the project of a new experimental facility to be installed at the Aerodynamics Division of the Institute of Aeronautics and Space is presented. This new facility will provide means to perform experimental campaigns to analyze the flow behavior at different rocket nozzle concepts using cold gas that will be obtained from a modification of the Pilot Transonic Wind Tunnel air system. The new installation will enable less expensive experiments in a more secure environment, since the cold gas experimental procedures do not demand fuel storage and burn and security procedures are much less severe. Furthermore, experiments can be carried with different types of sensors, commonly used in wind tunnel tests. Also, the optical access is facilitated enabling the use of optical techniques for the characterization of flow properties inside the nozzles, such as pressure and temperature sensitive painting. The full project design and the operation conditions will be showed, as also some technical considerations about the flor behavior in the facility

Dispositivo de microdescargas em gases na pressão atmosférica

This work describes the development of an electro-mechanical micro-discharges device operating at ambient condition of pressure and temperature, capable to produce plasma jets for surface finishing. The discharges are produced through a needle shape electrode hollow cathode type by which flows the helium gas. The voltage applied on the electrode is provided for an AC/AC switching voltage converter of full-bridge topology. The converter is energized by a power line of 110/220 VAC, 60 Hz and gives a 1000 V peak-to-peak from 5 kHz to 40 kHz square waveform output. The output frequency is defined by a control signal provided by an external signal generator. The equipment setup includes output acquisition of voltage and current and a photo-detector for photo-electrical measurements, which allows an optical characterization of the plasma jet

Projeto de adaptação do sistema de injeção do túnel transônico para ensaios em bocais de foguete

In this work, the project of a new experimental facility to be installed at the Aerodynamics Division of the Institute of Aeronautics and Space is presented. This new facility will provide means to perform experimental campaigns to analyze the flow behavior at different rocket nozzle concepts using cold gas that will be obtained from a modification of the Pilot Transonic Wind Tunnel air system. The new installation will enable less expensive experiments in a more secure environment, since the cold gas experimental procedures do not demand fuel storage and burn and security procedures are much less severe. Furthermore, experiments can be carried with different types of sensors, commonly used in wind tunnel tests. Also, the optical access is facilitated enabling the use of optical techniques for the characterization of flow properties inside the nozzles, such as pressure and temperature sensitive painting. The full project design and the operation conditions will be showed, as also some technical considerations about the flor behavior in the facility

Biomimetic Materials for Biomedical Applications

Objects with complex shape and functions have always attracted attention and interest. The morphological diversity and complexity of naturally occurring forms and patterns have been a motivation for humans to copy and adopt ideas from Nature to achieve functional, aesthetic and social value. Biomimetics is addressed to the design and development of new synthetic materials using strategies adopted by living organisms to produce biological materials. In particular, biomineralized tissues are often sophisticate composite materials, in which the components and the interfaces between them have been defined and optimized, and that present unusual and optimal chemical-physical, morphological and mechanical properties. Moreover, biominerals are generally produced by easily traceable raw materials, in aqueous media and at room pressure and temperature, that is through cheap process and materials. Thus, it is not surprising that the idea to mimic those strategies proper of Nature has been employed in several areas of applied sciences, such as for the preparation of liquid crystals, ceramic thin films computer switches and many other advanced materials. On this basis, this PhD thesis is focused on the investigation of the interaction of biologically active ions and molecules with calcium phosphates with the aim to develop new materials for the substitution and repair of skeletal tissue, according to the following lines: I. Modified calcium phosphates. A relevant part of this PhD thesis has been addressed to study the interaction of Strontium with calcium phosphates. It was demonstrated that strontium ion can substitute for calcium into hydroxyapatite, causing appreciable structural and morphological modifications. The detailed structural analysis carried out on the nanocrystals at different strontium content provided new insight into its interaction with the structure of hydroxyapatite. At variance with the behaviour of Sr towards HA, it was found that this ion inhibits the synthesis of octacalcium phosphate. However, it can substitute for calcium in this structure up to 15 atom %, in agreement with the increase of the cell parameters observed on increasing ion concentration. A similar behaviour was found for Magnesium ion, whereas Manganese inhibits the synthesis of octacalcium phosphate and it promotes the precipitation of dicalcium phosphate dehydrate. It was also found that Strontium affects the kinetics of the reaction of hydrolysis of α-TCP. It inhibits the conversion from α-TCP to hydroxyapatite. However, the resulting apatitic phase contains significant amounts of Sr2+ suggesting that the addition of Sr2+ to the composition of α-TCP bone cements could be successfully exploited for its local delivery in bone defects. The hydrolysis of α-TCP has been investigated also in the presence of increasing amounts of gelatin: the results indicated that this biopolymer accelerates the hydrolysis reaction and promotes the conversion of α-TCP into OCP, suggesting that its addition in the composition of calcium phosphate cements can be employed to modulate the OCP/HA ratio, and as a consequence the solubility, of the set cement. II. Deposition of modified calcium phosphates on metallic substrates. Coating with a thin film of calcium phosphates is frequently applied on the surface of metallic implants in order to combine the high mechanical strength of the metal with the excellent bioactivity of the calcium phosphates surface layers. During this PhD thesis, thank to the collaboration with prof. I.N. Mihailescu, head of the Laser-Surface-Plasma Interactions Laboratory (National Institute for Lasers, Plasma and Radiation Physics – Laser Department, Bucharest) Pulsed Laser Deposition has been successfully applied to deposit thin films of Sr substituted HA on Titanium substrates. The synthesized coatings displayed a uniform Sr distribution, a granular surface and a good degree of crystallinity which slightly decreased on increasing Sr content. The results of in vitro tests carried out on osteoblast-like and osteoclast cells suggested that the presence of Sr in HA thin films can enhance the positive effect of HA coatings on osteointegration and bone regeneration, and prevent undesirable bone resorption. The possibility to introduce an active molecule in the implant site was explored using Matrix Assisted Pulsed Laser Evaporation to deposit hydroxyapatite nanocrystals at different content of alendronate, a bisphosphonate widely employed in the treatments of pathological diseases associated to bone loss. The coatings displayed a good degree of crystallinity, and the results of in vitro tests indicated that alendronate promotes proliferation and differentiation of osteoblasts even when incorporated into hydroxyapatite. III. Synthesis of drug carriers with a delayed release modulated by a calcium phosphate coating. A core-shell system for modulated drug delivery and release has been developed through optimization of the experimental conditions to cover gelatin microspheres with a uniform layer of calcium phosphate. The kinetics of the release from uncoated and coated microspheres was investigated using aspirin as a model drug. It was shown that the presence of the calcium phosphate shell delays the release of aspirin and allows to modulate its action.

Genesis of metasomatic sapphirine-corundum-spinel-bearing granulites in Sri Lanka

The goal of the present study is to understand the mechanism of mass transfer, the composition and the role of fluids during crustal metasomatism in high-temperature metamorphic terranes. A well constrained case study, a locality at Rupaha, Sri Lanka was selected. It is located in the Highland Complex of Sri Lanka, which represents a small, but important fragment of the super-continent Gondwana. Excellent exposures of ultramafic rocks, which are embedded in granulites, were found at 10 localities. These provide a unique background for understanding the metasomatic processes. The boundary between the ultramafic and the granulite rocks are lined with metasomatic reaction zones up to 50cm in width. Progressing from the ultramafics to the granulite host rock, three distinct zones with the following mineral assemblages can be distinguished: (1). phlogopite + spinel + sapphirine, (2). spinel + sapphirine and (3). corundum + biotite + plagioclase. In order to assess the P-T-t path, the peak metamorphism and the exhumation history were constrained using different thermobarometers, as well as a diffusion model of garnet zoning. A maximum temperature of 875 ± 20oC (Opx-Cpx thermometer) and at the peak pressure of 9.0 ± 0.1 kbar (Grt-Cpx-Pl-Qtz) was calculated for the silicic granulite. The ultramafic rocks recorded a peak temperature of 840 ± 70oC (Opx-Cpx thermometer) at 9 kbar. Coexisting spinel and sapphirine from the reaction zone yield a temperature of 820 ± 40oC. This is in agreement with the peak-temperatures recorded in the adjacent granulites and ultramafics rocks. The structural concordance of the ultramafic rocks with the siliceous granulite host rock further support the suggestion, that all units have experienced the same peak metamorphism. Diffusion modeling of retrograde zoning in garnets from mafic granulites suggests a three-step cooling history. A maximum cooling rate of 1oC/Ma is estimated during the initial stage of cooling, followed by a cooling rate of ~30oC/Ma. The outermost rims of garnet indicate a slightly slower cooling rate at about 10-15oC/Ma. The sequences of mineral zones, containing a variety of Al-rich, silica undersaturated minerals in the reaction zones separating the ultramafic rocks from the silica-rich rocks can be explained by a diffusion model. This involves the diffusion of Mg from ultramafic rocks across the layers, and K and Si diffuse in opposite direction. Chemical potential of Mg and Si generated continuous monotonic gradient, allowing steady state diffusional transport across the profile. The strong enrichment in Al, and the considerable loss of Si, during the formation of reaction bands can be inferred from isocon diagrams. Some Al was probably added to the reaction zones, while Si was lost. This is most likely due to fluids percolating parallel to the zones at the boundary of the rock units. This study has shown that not only pressure and temperature conditions but most importantly PH2O and the concentration of the chlorine and fluorine in aqueous fluids also control the mass transport in different geological environments.

Klonierung und Charakterisierung der Luziferase und des Luziferin regenerierenden Enzyms aus dem marinen Schwamm Suberites domuncula

Bereits 1971 erkannte Reiswig bei einigen Schwämmen in der Kontraktion des Osculums eine Reaktion auf Licht. Nachfolgend konnte für eine Reihe von Schwämmen die Existenz von Lichtreaktionen beobachtet werden (Wapstra & van Soest, 1987). In dieser Arbeit sollten Gene eines Luziferin/Luziferase Systems im marinen Schwamm Suberites domuncula identifiziert werden, die eine Rolle bei der Bio¬lumineszenz spielen. Mit Hilfe der PCR-Technik konnten die in der cDNA-Bank identifizierten Fragmente einer Luziferase und eines Luziferin regenerierenden Enzyms erfolgreich vervollständigt, kloniert und analysiert werden. Datenbank¬analysen der abgeleiteten Aminosäuresequenzen ergeben sowohl für die Luziferase als auch für das Luziferin regenerierende Enzym Ähnlichkeiten zu den entsprechenden Proteinen aus Leuchtkäfern, wie z. B. Photinus pyralis. Ausgehend von der cDNA wurden zunächst beide Enzyme in E. coli rekombinant exprimiert und affinitätschromatographisch aufgereinigt. Für die Luziferase gelang es, spezifische Antikörper herzustellen, die im Anschluss an den im Western Blot durchgeführten Nachweis eine Identifizierung in histologischen Schwamm¬schnitten ermöglichte. Weitere Analysen konnten für Suberites domuncula sowohl im Schwammgewebe, im Proteinextrakt als auch für das rekombinante Protein die Licht-generierende Fähigkeit nachweisen. Das ermittelte in vitro Biolumineszenz-Emissionsspektrum der rekombinanten Luziferase weist eine Lichtemission im gelb-grünen Bereich des Spektrums mit einem Maximum bei 548 nm und einer Schulter bei 590 nm auf. Ausserdem bestätigte die Funktionanalyse des rekombinanten Enzyms die für Luziferasen bekannte ATP- und Temperatur¬abhängigkeit sowie den stimulierenden Effekt von Coenzym A. Die Existenz einer bioaktiven Luziferase in einem der ältesten, rezent vertretenen Metazoa deutet darauf hin, dass sich die Oxygenasefunktion der Luziferasen bereits früher entwickelte, als bisher von Viviani* vermutet. Die bisherigen Daten über die optischen Eigenschaften der Spiculae liefern gemeinsam mit den Ergebnissen dieser Arbeit – einer Licht-emittierenden Luziferase in S. domuncula – die Voraussetzungen für die mögliche Existenz eines Photorezeptionssystems in Schwämmen.

Entwicklung einer Thermodesorptionseinheit für die GC/MS zur Bestimmung hochreaktiver, biogener Kohlenwasserstoffe und deren Anwendung im Rahmen von Labor- und Feldstudien

Flüchtige organische Verbindungen (volatile organic compounds, VOCs), besonders rnTerpene, gelten als Vorläufer des sekundären organischen Aerosols (secondary rnorganic aerosols, SOA). Terpene werden von Pflanzen zur Abwehr oder zur rnAttraktion von Bestäubern emittiert. Ungesättigten Verbindungen, wie Sesquiterpene, rnsind sehr ozonolyseempfindlich und weisen nur geringe Konzentrationen in der rnAtmosphäre auf. Zudem lassen sie sich mit handelsüblichen rnThermodesorptionseinheiten meist nicht ohne Artefakte nachweisen, da sie eine hohe rnReaktivität mit vielen Oberflächen zeigen. rnDiese Arbeit präsentiert Forschungsergebnisse der qualitativen und rn(semi)quantitativen Auswertungen flüchtiger organischer Verbindungen in rnLaborstudien und biogenen Emissionsproben (Feldmessungen) mittels rnThermodesorption-Gaschromatographie-Massenspektrometrie (TD-GC/MS). Speziell rnzur Analyse hochreaktiver Verbindungen wurde eine Thermodesorptionseinheit für die rnGC/MS entwickelt. Diese besteht aus einer Kryofokussierung, einem Desorptionsofen rnund einer Heizung. Die Steuerung erfolgt über eine eigens dafür geschaffene rnBedienoberf läche von Labview® an einem PC über eine nachgeschaltete SPS rn(speicherprogrammierbare Steuerung). Das komplette Desorptionsprogramm und der rnStart der GC/MS-Analyse wurden automatisiert. rnDie Quantifizierung alle Proben wurde über Diffusionsquellen und rnVergleichsmessungen durch auf Adsorptionsröhrchen aufgebrachte rnVerdünnungsreihen realisiert. Um Informationen über die mutmaßlichen Vorläufer des rnsekundären organischen Aerosols zu erhalten, wurde zudem eine Ozon-Scrubber-rnMethode basierend auf Propen entwickelt. Diese wurde anhand von Standards in einer rnReaktionskammer getestet und in Feldmessungen erfolgreich angewendet. rnQuantitative Analysen zeigen, dass die meisten Terpene so vollständig vor der rnOzonolyse bewahrt werden können. Für hochreaktive Analyte wie α-Humulen oder rnβ-Caryophyllen wurden Wiederfindungsraten von über 80 % erreicht. So konnte die rnTemperaturabhängigkeit der Terpen-Emissionen der Fichte (Picea abies) in rnFeldmessungen nachgewiesen werden. rnEine weitere Anwendungsmöglichkeit wurde mit der Unterscheidung verschiedener rnArten der gleichen Gattung anhand der Emissionsmuster und der möglichen rnAbgrenzung verschiedener Bestäubertypen am Beispiel der Gattung Salvia untersucht. rnDie Emissionsanalysen zeigen, dass eine Zuordnung der Verwandtschaftsverhältnisse rnzusätzlich zu anderen Vergleichen möglich ist. Das gleiche gilt für die Differenzierung rnvon Bestäubertypen. Die Ergebnisse der Feldmessungen wurden durch rnMethodenvergleich zwischen biogenen Emissionsmessungen mit anschließender rnTD-GC/MS-Analyse und Extraktionen der jeweiligen Blüten/Blätter mit rnanschließender GC/MS-Messung bestätigt.

Thermoelectric properties in phase-separated half-Heusler materials

The conversion of dissipated heat into electricity is the basic principle of thermoelectricity. In this context, half-Heusler (HH) compounds are promising thermoelectric (TE) materials for waste heat recovery. They meet all the requirements for commercial TE applications, ranging from good efficiencies via environmentally friendliness to being low cost materials. This work focused on the TE properties of Ti0.3Zr0.35Hf0.35NiSn-based HH materials. This compound undergoes an intrinsic phase separation into a Ti-poor and Ti-rich HH phase during a rapid solidification process. The resulting dendritic microstructure causes a drastic reduction of the thermal conductivity, leading to higher TE efficiencies in these materials. The TE properties and temperature dependence of the phase-separated Ti0.3Zr0.35Hf0.35NiSn compound were investigated. The TE properties can be adjusted depending on the annealing treatment. The extension of annealing time for 21 days at 1000 °C revealed a reduction of the thermal conductivity and thus an enhancement of the TE performance in this sample. An increase of annealing temperature caused a change of the phase fraction ratio in favor of the Ti-rich phase, leading to an improvement of the electronic properties. rnInspired by the TE properties of the Ti0.3Zr0.35Hf0.35NiSn HH compound, the performance of different n- and p-type materials, realized via site substitution with donor and acceptor elements was examined. The fabrication of a TE n- and p-type material pair based on one starting compound can guarantee similar TE and mechanical properties and is enormous beneficial for device engineering. As donor dopants V, Nb and Sb were tested. Depending on the lattice position small doping levels were sufficient to attain distinct improvement in their TE efficiency. Acceptor-induced doping with Sc, Y and Co caused a change in the transport behavior from n- to p- type conduction, revealing the highest Seebeck coefficients obtained in the MNiSn system. rnThen, the long-term stability of an exemplary n- and p-type HH compound was proven. Surprisingly, the dendritic microstructure can be maintained even after 500 cycles (1700 h) from 373 to 873 K. The TE performance of both n- and p-type materials showed no significant change under the long-term treatment, indicating the extraordinary temperature stability of these compounds. Furthermore both HH materials revealed similar temperature-dependence of their mechanical properties. This work demonstrates the excellent suitability of phase-separated HH materials for future TE applications in the moderate temperature range.rn

Prediction of new crystal structures under extreme conditions

One of the most important challenges in chemistry and material science is the connection between the contents of a compound and its chemical and physical properties. In solids, these are greatly influenced by the crystal structure.rnrnThe prediction of hitherto unknown crystal structures with regard to external conditions like pressure and temperature is therefore one of the most important goals to achieve in theoretical chemistry. The stable structure of a compound is the global minimum of the potential energy surface, which is the high dimensional representation of the enthalpy of the investigated system with respect to its structural parameters. The fact that the complexity of the problem grows exponentially with the system size is the reason why it can only be solved via heuristic strategies.rnrnImprovements to the artificial bee colony method, where the local exploration of the potential energy surface is done by a high number of independent walkers, are developed and implemented. This results in an improved communication scheme between these walkers. This directs the search towards the most promising areas of the potential energy surface.rnrnThe minima hopping method uses short molecular dynamics simulations at elevated temperatures to direct the structure search from one local minimum of the potential energy surface to the next. A modification, where the local information around each minimum is extracted and used in an optimization of the search direction, is developed and implemented. Our method uses this local information to increase the probability of finding new, lower local minima. This leads to an enhanced performance in the global optimization algorithm.rnrnHydrogen is a highly relevant system, due to the possibility of finding a metallic phase and even superconductor with a high critical temperature. An application of a structure prediction method on SiH12 finds stable crystal structures in this material. Additionally, it becomes metallic at relatively low pressures.