Influência da temperatura e do pH do meio sobre a resistência à corrosão das ligas Al(20204-T3), Al(7010-T7) e Al(7050-T7) utilizadas na indústria aeronáutica

Pós-graduação em Engenharia Mecânica - FEG

Estudo da velocidade de despassivação de aços em estruturas de concreto armado, em meio de cloreto

The aim of the present study was to investigate the corrosion resistance in chloride medium of two cylindrical steel samples from civil construction (CA-50 and CA-60). For this purpose, electrochemical measurements were performed in NaCl solution, 4.0 g/L, naturally aerated. According to electrochemical responses, it was observed an active dissolution process at open circuit potential for both steels. In this comparative study, the differences between CA-50 and CA60 were not significant, since the values of polarization resistance estimated by EIS were the same order of magnitude for both types of steel (oscillating between 200 and 500 Ohm). For all evaluated thicknesses of concrete reinforcement, these values ranged between 2 and 9 kOhm, and the lower value was associated with lower thickness, particularly at 7, 21 and 35 days. When these results were compared with those determined for the CA-60, it was found that the layer of concrete reinforcement provide a protection against corrosion in chloride medium at least ten times larger

Solution heat treatment of plasma nitrided 15-5PH stainless steel - Part I: Improvement of the corrosion resistance

The results of the investigation on Solution Heat Treatment of Plasma Nitrided (SHTPN) precipitation-hardened steel 15-5PH are presented. The layers have been obtained by the plasma nitriding process followed by solution heat treatment at different temperatures. The influence of the solution heat treatment after nitriding on the dissolution process of the nitrided layer has been considered. The nitrided layers were studied by scanning electron microscopy, X-ray microanalysis (EDX), and X-Ray diffraction. Micro-hardness tests of the nitrided layers and solubilized nitrided layers have been carried out and interpreted by considering the processing conditions. It was found that high nitrogen austenitic cases could be obtained after SHTPN of martensitic precipitation-hardened steel (15-5PH). When Solution Heat Treatment (SHT) was performed at 1100 °C, some precipitates were observed. The amount of precipitates significantly reduced when the temperature increased. The EDX microanalysis indicated that the precipitate may be chromium niobium nitride. When the precipitation on the austenite phase occurred in small amount, the corrosion resistance increased in SHTPN specimens and the pit nucleation potential also increased. The best corrosion result occurred for SHT at 1200 °C.

Estudo da reação de dissolução de serpentinitos brasileiros para uso em processo de captura de carbono

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência da Motilidade Gastrintestinal no processo de desintegração de comprimidos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

NMR spectroscopy and imaging of hyperpolarized gases

Since the discovery of the nuclear magnetic resonance (NMR) phenomenon, countless NMR techniques have been developed that are today indispensable tools in physics, chemistry, biology, and medicine. As one of the main obstacles in NMR is its notorious lack of sensitivity, different hyperpolarization (HP) methods have been established to increase signals up to several orders of magnitude. In this work, different aspects of magnetic resonance, using HP noble gases, are studied, hereby combining different disciplines of research. The first part examines new fundamental effects in NMR of HP gases, in theory and experiment. The spin echo phenomenon, which provides the basis of numerous modern experiments, is studied in detail in the gas phase. The changes of the echo signal in terms of amplitude, shape, and position, due to the fast translational motion, are described by an extension of the existing theory and computer simulations. With this knowledge as a prerequisite, the detection of intermolecular double-quantum coherences was accomplished for the first time in the gas phase. The second part of this thesis focuses on the development of a practical method to enhance the dissolution process of HP 129Xe, without loss of polarization or shortening of T1. Two different setups for application in NMR spectroscopy and magnetic resonance imaging (MRI) are presented. The continuous operation allows biological and multidimensional spectroscopy in solutions. Also, first in vitro MRI images with dissolved HP 129Xe as contrast agent were obtained at a clinical scanner.

Andrea Branzi y la “Città senza architettura”: De la No-Stop City a los modelos de urbanización débil

El tema de estudio de esta tesis son las propuestas urbanas que Andrea Branzi ha desarrollado durante los últimos cincuenta años, centrándose especialmente en aquellas más elaboradas y completas: la No-Stop City (1970-71), que elabora como miembro del grupo radical Archizoom, y dos de sus modelos de urbanización débil, Agronica (1995) y el Master Plan para el Strijp Philips de Eindhoven (2000). Se trata de una parte de su obra que ha mantenido constante, a lo largo del tiempo, una propuesta de disolución de la arquitectura de notable consistencia que puede describirse con la fórmula “città senza architettura”, acuñada por él mismo. Una voluntad que ya se apunta en la muy variada producción de Archizoom previa a la No-Stop City, y que cristaliza y se hace explícita en este proyecto que aspiraba a: “liberar al hombre de la arquitectura”. A pesar de la continuidad de esta idea en el tiempo, la ciudad sin arquitectura de Branzi ha evolucionado claramente dando lugar a distintos tipos de disolución. Una disolución que, obviamente, no supone la efectiva desaparición de la disciplina, sino la formulación de una arquitectura “otra” basada en un replanteamiento radical de la naturaleza y el papel de la misma. Esta agenda contra la disciplina se ha desplegado a través de una serie de temas que socavan el objeto arquitectónico canónico (su vaciamiento expresivo, la pérdida de importancia de la envolvente y la forma acabada, el carácter anticompositivo, la independencia entre forma y función, la mutabilidad en el tiempo…), pero va más allá al poner en crisis el rol que la propia arquitectura ha tenido en la configuración material, política y simbólica del hábitat humano. Una pérdida de protagonismo y centralidad en la sociedad contemporánea que, en el discurso del arquitecto, implica necesariamente un papel subordinado. De este proceso de disolución surge un nuevo tipo de ciudad en la que la forma urbana o se ha perdido o se ha convertido en superflua, en la que se ha disuelto la zonificación funcional, cuyos espacios interiores se hallan en un proceso de permanente reprogramación que ignora las tipologías, que trasciende la división entre lo urbano y lo agrícola y que es, ante todo, un espacio de flujos y servicios. La crisis de la ciudad tradicional implica, en definitiva, un cambio en la naturaleza misma de lo urbano que pasa de considerarse un lugar físico y construido, a convertirse en una condición inmaterial y virtualmente omnipresente que se despliega independientemente de su soporte físico. En las investigaciones urbanas de Branzi convergen, además, muchas de las reflexiones que el arquitecto ha desarrollado sobre, y desde, las distintas “escalas” de la actividad profesional: diseño, arquitectura y urbanismo. Estas propuestas no sólo cuestionan las relaciones establecidas entre objetos, edificios, ciudades y territorios sino que ponen en cuestión estas mismas categorías. Unas ciudades sin arquitectura que se basan, en última instancia, en plantear preguntas que son muy sencillas y, por otra parte, eternas: ¿Qué es un edificio? ¿Qué es una ciudad? ABSTRACT The subject of study of this thesis are the urban proposals developed by Andrea Branzi over the last fifty years, with a special focus on the more developed and comprehensive ones: the No- Stop City (1970-1971), produced as a member of the architettura radicale group Archizoom, and two of his “weak urbanization models”: Agronica (1995) and the Master Plan for Philips Strijp in Eindhoven (2000). This area of his work has kept, over time, a remarkably consistent proposal for the dissolution of architecture that can be described with the motto città senza architettura (city without architecture), coined by himself. A determination, already latent in the very diverse production of Archizoom prior to No-Stop City, that crystallizes and becomes explicit in this project which was aimed to "liberate man from the architecture." Despite the continuity of this idea over time, Branzi’s city without architecture has clearly evolved leading to different types of dissolution. A dissolution that, obviously, does not mean the effective demise of the discipline, but rather, the formulation of an architecture autre based on a radical rethinking of its nature and role. This agenda against the discipline has been developed through a number of issues that undermine the canonical architectural object (its expressive emptying, the loss of importance of the envelope and the finished shape, the anticompositional character, the independence between form and function, the mutability over time...), but goes beyond it by putting into crisis the role that architecture itself has had in the material, political and symbolic configuration of the human habitat. A loss of prominence and centrality in contemporary society that, in the architect’s discourse, implies a subordinate role. From this dissolution process, a new type of city arises: a city where urban form has been lost or has become superfluous, in which functional zoning has dissolved, whose interiors are in a permanent process of reprogramming that ignores typologies, that transcends the division between urban and agricultural and becomes, above all, a space of flows and services. Ultimately, the crisis of the traditional city implies a change in the very nature of the urban that moves from being regarded as a physical and built place, to become an immaterial and virtually omnipresent condition that unfolds regardless of its physical medium. Many of the ideas Branzi has developed on, and from, the different "scales" of professional activity (design, architecture and urbanism) converge in his urban research. These proposals not only question the relations between objects, buildings, cities and territories but also these very categories. Cities without architecture that are based, ultimately, on raising simple questions that are, on the other hand, eternal: What is a building? What is a city?

Plastisol gelation and fusion rheological aspects

This study deals with the rheological aspects of poly-vinyl chloride (PVC) plastisol gelation and fusion processes in foamable formulations. Here, such processes are simulated by temperature-programmed experiment (5 K min−1) in which complex viscosity components are continuously recorded. Nineteen samples based on a PVC-VAC (vinyl acetate 95/5) copolymer with 100 phr plasticizer have been studied, differing only by the plasticizer structure. The sample shear modulus increases continuously with temperature until a maximum, long time after the end of the dissolution process as characterized by DSC. The temperature at the maximum varies between 345 and 428 K with a clear tendency to increase almost linearly with the plasticizer molar mass, and to vary with the flexibility and the degree of branching of the plasticizer molecule. The shear modulus increase is interpreted in terms of progressive “welding” of swelled particles by polymer chain reptation. The plasticizer nature would mainly affect the friction parameter of chain diffusion.

Sedimentation rates calculated on surface sediment samples from different site of the Atlantic and Pacific Oceans (Table 1)

Radiocarbon ages on CaCO3 from deep-sea cores offer constraints on the nature of the CaCO3 dissolution process. The idea is that the toll taken by dissolution on grains within the core top bioturbation zone should be in proportion to their time of residence in this zone. If so, dissolution would shift the mass distribution in favor of younger grains, thereby reducing the mean radiocarbon age for the grain ensemble. We have searched in vain for evidence supporting the existence of such an age reduction. Instead, we find that for water depths of more than 4 km in the tropical Pacific the radiocarbon age increases with the extent of dissolution. We can find no satisfactory steady state explanation and are forced to conclude that this increase must be the result of chemical erosion. The idea is that during the Holocene the rate of dissolution of CaCO3 has exceeded the rain rate of CaCO3. In this circumstance, bioturbation exhumes CaCO3 from the underlying glacial sediment and mixes it with CaCO3 raining from the sea surface.

Solid dispersions: formulation, characterisation, permeability and genomic evaluation

Poor water solubility is characterised by low dissolution rate and consequently reduced bioavailability. Formulation of solid dispersion of the drug has attracted considerable interest as a means of improving dissolution process of a range of poorly water soluble drugs. This current study investigates the formulation of solid dispersion for a range of poorly water soluble drugs with varying physicochemical properties including paracetamol, sulphamethoxazole, phenacetin, indomethacin, chloramphenicol, phenylbutazone and succinylsulphathiazole. Solid dispersions were prepared using various drugs to polymer ratios. PEG 8000 was selected as a carrier in the solid dispersions. The study revealed that inclusion of drug within the polymeric matrix, ratio of drug to polymer and physicochemical properties of the drug molecules enhance the dissolution rate. Characterisations of the solid dispersions were performed using DSC, FTIR and SEM. These studies revealed that all seven drugs were present in the amorphous form within the solid dispersions and there was a lack of interaction between the PEG 8000 and drug. Stability studies for solid dispersions showed that all seven drugs studied were unstable at accelerated conditions (40°C±2°C/75%RH±5%RH) whereas, they were found to be stable for 12 months at room conditions. Permeability of indomethacin, phenacetin, phenylbutazone and paracetamol were higher for solid dispersions as compared to drug alone across Caco-2 cell monolayers. From the cell uptake studies it was shown that PEG 8000 enhanced rhodamine123 uptake which suggested that PEG 8000 may increase the permeability of these drugs in solid dispersions. Gene expression profiles analyzing the expression changes in the ABC and solute carrier transporter during permeability studies.ABCA10, ABCB4, ABCC12, SLC12A6, MCT13, SLC22A12 and SLC6A6 gene expression were increased by indomethacin alone whereas solid dispersion of indomethacin resulted in a slight increase in expression. ABCC12 and SAMC gene expression was increased in case of paracetamol alone but slightly increased when exposed to solid dispersion of paracetamol.

Seawater carbonate chemistry and calcification during experiments with coral communities, 2002

The effect of increased CO2 partial pressure (pCO2) on the community metabolism (primary production, respiration, and calcification) of a coral community was investigated over periods ranging from 9 to 30 d. The community was set up in an open-top mesocosm within which pCO2 was manipulated (411, 647, and 918 µatm). The effect of increased pCO2 on the rate of calcification of the sand area of the mesocosm was also investigated. The net community primary production (NCP) did not change significantly with respect to pCO2 and was 5.1 ± 0.9 mmol O2 m-2 h-1, Dark respiration (R) increased slightly during the experiment at high pCO2, but this did not affect significantly the NCP:R ratio (1.0 ± 0.2). The rate of calcification exhibited the trend previously reported; it decreased as a function of increasing pCO2 and decreasing aragonite saturation state. This re-emphasizes the predictions that reef calcification is likely to decrease during the next century. The dissolution process of calcareous sand does not seem to be affected by open seawater carbonate chemistry; rather, it seems to be controlled by the biogeochemistry of sediment pore water.

Zn/Sr record of the Last Interglacial Transition in South Atlantic Ocean sediments

We examined the zinc content of diatom frustules as an indicator of past changes in surface seawater Zn2+ concentration. Zn/Si data of samples from three cores located in the South Atlantic sector of the Southern Ocean spanning the last interglacial-glacial transition are presented. Changes in the Zn/Si record are linked to changes in the surface water Zn2+ concentration. The source of variation in Zn2+ concentration appears to be via changes in deep water upwelling and circulation. We rule out changes in phytoplankton productivity and aeolian dust input as a source of variation in the Zn/Si record. Likewise, the Zn/Si data are not linked to shifts in the diatom species composition of the sediment or sediment preservation effects. The Zn/Si results presented do not support the zinc hypothesis. There is no link between the uptake of CO2 by phytoplankton, as inferred from the d13C record, and the Zn/Si record.

Solubility and solvation of monosaccharides in ionic liquids

Herein, solubility experimental data for six monosaccharides, viz. D-(+)-glucose, D-(+)-mannose, D-(-)-fructose, D-(+)-galactose, D-(+)-xylose and L-(+)-arabinose, in four ionic liquids (ILs), at temperatures ranging from 288.2 to 348.2 K, were obtained aimed at gathering a better understanding of their solvation ability and molecular-level mechanisms which rule the dissolution process. To ascertain the chemical features that enhance the solubility of monosaccharides, ILs composed of dialkylimidazolium or tetra-alkylphosphonium cations combined with the dicyanamide, dimethylphosphate or chloride anions were investigated. It was found that the ranking of the solubility of monosaccharides depends on the IL; yet, D-(+)-xylose is always the most soluble while D-(-)-fructose is the least soluble monosaccharide. The results obtained show that both the IL cation and the anion play a major role in the solubility of monosaccharides. Finally, from the determination of the respective thermodynamic properties of solution, it was found that enthalpic contributions are dominant in the solubilization process. However, the observed differences in the solubilities of monosaccharides in 1-butyl-3-methylimidazolium dicyanamide are ruled by a change in the entropy of solution.

The Rapakivi texture of feldspars in a plutonic mixing environment - A dissolution-recrystallization process

A new hypothesis is formulated to explain the development of rapakivi texture in and around the mafic enclaves of porphyritic granitoids, i.e. in environments involving magma mixing and mingling. The formation of a plagioclase mantle around alkali feldspar megacrysts is attributed to the localized presence of a melt resulting from the reaction of these megacrysts, with host hybrid magma with which they are in disequilibrium. This feldspathic melt adheres to the resorbed crystals and is virtually immiscible with the surrounding magma. Its composition is modified in terms of the relative proportions of K2O, Na2O, and CaO through selective diffusion of these elements, thus allowing the specific crystallization of andesine. With decreasing temperature, the K-feldspar, again stable, crystallizes along with the plagioclase, leading to mixed mantle structures.

Physicochemical and dissolution profile characterization of pellets containing different binders obtained by the extrusion-spheronization process

With the purpose of evaluating the behavior of different polymers employed as binders in small-diameter pellets for oral administration, we prepared formulations containing paracetamol and one of the following polymers: PVP, PEG 1500, hydroxypropylmethylcellulose and methylcellulose, and we evaluated their different binding properties. The pellets were obtained by the extrusion/spheronization process and were subsequently subjected to fluid bed drying. In order to assess drug delivery, the United States Pharmacopeia (USP) apparatus 3 (Bio-Dis) was employed, in conjunction with the method described by the same pharmacopeia for the dissolution of paracetamol tablets (apparatus 1). The pellets were also evaluated for granulometry, friability, true density and drug content. The results indicate that the different binders used are capable of affecting production in different ways, and some of the physicochemical characteristics of the pellets, as well as the dissolution test, revealed that the formulations acted like immediate-release products. The pellets obtained presented favorable release characteristics for orally disintegrating tablets. USP apparatus 3 seems to be more adequate for discriminating among formulations than the basket method.