Desenvolvimento de sistemas de aditivos químicos para aplicação em cimentações de poços de petróleo

The primary cementing is an important step in the oilwell drilling process, ensuring the mechanical stability of the well and the hydraulic isolation between casing and formation. For slurries to meet the requirements for application in a certain well, some care in the project should be taken into account to obtain a cement paste with the proper composition. In most cases, it is necessary to add chemicals to the cement to modify its properties, according to the operation conditions and thus obtain slurries that can move inside the jacket providing a good displacement to the interest area. New technologies of preparation and use of chemicals and modernization of technological standards in the construction industry have resulted in the development of new chemical additives for optimizing the properties of building materials. Products such as polycarboxylate superplasticizers provide improved fluidity and cohesion of the cement grains, in addition to improving the dispersion with respect to slurries without additives. This study aimed at adapting chemical additives used in civil construction to be used use in oilwell cement slurries systems, using Portland cement CPP-Special Class as the hydraulic binder. The chemical additives classified as defoamer, dispersant, fluid loss controller and retarder were characterized by infrared absorption spectroscopy, thermogravimetric analyses and technological tests set by the API (American Petroleum Institute). These additives showed satisfactory results for its application in cement slurries systems for oil wells. The silicone-based defoamer promoted the reduction of air bubbles incorporated during the stirring of the slurries. The dispersant significantly reduced the rheological parameters of the systems studied. The tests performed with the fluid loss controller and the retarder also resulted in suitable properties for application as chemical additives in cement slurries

Stranski-Krastanov InN/InGaN quantum dots grown directly on Si(111)

The authors discuss and demonstrate the growth of InN surface quantum dots on a high-In-content In0.73Ga0.27N layer, directly on a Si(111) substrate by plasma-assisted molecular beam epitaxy. Atomic force microscopy and transmission electron microscopy reveal uniformly distributed quantum dots with diameters of 10–40 nm, heights of 2–4 nm, and a relatively low density of ∼7 × 109 cm−2. A thin InN wetting layer below the quantum dots proves the Stranski-Krastanov growth mode. Near-field scanning optical microscopy shows distinct and spatially well localized near-infrared emission from single surface quantum dots. This holds promise for future telecommunication and sensing devices.

Two roads to planet detection

One of the most exciting discoveries in astrophysics of the last last decade is of the sheer diversity of planetary systems. These include "hot Jupiters", giant planets so close to their host stars that they orbit once every few days; "Super-Earths", planets with sizes intermediate to those of Earth and Neptune, of which no analogs exist in our own solar system; multi-planet systems with planets smaller than Mars to larger than Jupiter; planets orbiting binary stars; free-floating planets flying through the emptiness of space without any star; even planets orbiting pulsars. Despite these remarkable discoveries, the field is still young, and there are many areas about which precious little is known. In particular, we don't know the planets orbiting Sun-like stars nearest to our own solar system, and we know very little about the compositions of extrasolar planets. This thesis provides developments in those directions, through two instrumentation projects.

The first chapter of this thesis concerns detecting planets in the Solar neighborhood using precision stellar radial velocities, also known as the Doppler technique. We present an analysis determining the most efficient way to detect planets considering factors such as spectral type, wavelengths of observation, spectrograph resolution, observing time, and instrumental sensitivity. We show that G and K dwarfs observed at 400-600 nm are the best targets for surveys complete down to a given planet mass and out to a specified orbital period. Overall we find that M dwarfs observed at 700-800 nm are the best targets for habitable-zone planets, particularly when including the effects of systematic noise floors caused by instrumental imperfections. Somewhat surprisingly, we demonstrate that a modestly sized observatory, with a dedicated observing program, is up to the task of discovering such planets.

We present just such an observatory in the second chapter, called the "MINiature Exoplanet Radial Velocity Array," or MINERVA. We describe the design, which uses a novel multi-aperture approach to increase stability and performance through lower system etendue, as well as keeping costs and time to deployment down. We present calculations of the expected planet yield, and data showing the system performance from our testing and development of the system at Caltech's campus. We also present the motivation, design, and performance of a fiber coupling system for the array, critical for efficiently and reliably bringing light from the telescopes to the spectrograph. We finish by presenting the current status of MINERVA, operational at Mt. Hopkins observatory in Arizona.

The second part of this thesis concerns a very different method of planet detection, direct imaging, which involves discovery and characterization of planets by collecting and analyzing their light. Directly analyzing planetary light is the most promising way to study their atmospheres, formation histories, and compositions. Direct imaging is extremely challenging, as it requires a high performance adaptive optics system to unblur the point-spread function of the parent star through the atmosphere, a coronagraph to suppress stellar diffraction, and image post-processing to remove non-common path "speckle" aberrations that can overwhelm any planetary companions.

To this end, we present the "Stellar Double Coronagraph," or SDC, a flexible coronagraphic platform for use with the 200" Hale telescope. It has two focal and pupil planes, allowing for a number of different observing modes, including multiple vortex phase masks in series for improved contrast and inner working angle behind the obscured aperture of the telescope. We present the motivation, design, performance, and data reduction pipeline of the instrument. In the following chapter, we present some early science results, including the first image of a companion to the star delta Andromeda, which had been previously hypothesized but never seen.

A further chapter presents a wavefront control code developed for the instrument, using the technique of "speckle nulling," which can remove optical aberrations from the system using the deformable mirror of the adaptive optics system. This code allows for improved contrast and inner working angles, and was written in a modular style so as to be portable to other high contrast imaging platforms. We present its performance on optical, near-infrared, and thermal infrared instruments on the Palomar and Keck telescopes, showing how it can improve contrasts by a factor of a few in less than ten iterations.

One of the large challenges in direct imaging is sensing and correcting the electric field in the focal plane to remove scattered light that can be much brighter than any planets. In the last chapter, we present a new method of focal-plane wavefront sensing, combining a coronagraph with a simple phase-shifting interferometer. We present its design and implementation on the Stellar Double Coronagraph, demonstrating its ability to create regions of high contrast by measuring and correcting for optical aberrations in the focal plane. Finally, we derive how it is possible to use the same hardware to distinguish companions from speckle errors using the principles of optical coherence. We present results observing the brown dwarf HD 49197b, demonstrating the ability to detect it despite it being buried in the speckle noise floor. We believe this is the first detection of a substellar companion using the coherence properties of light.

Estructuras sub-longutud de onda para el diseño de dispositivos en guía dieléctrica

Sub-wavelength structures are enabling the design of devices based in dielectric waveguides with unprecedented performance in both the near-infrared and mid-infrared wavelength regions. These devices include fiber-to-chip grating couplers with sub-decibel efficiency, waveguide couplers with bandwidths of several hundred nanometers, and low loss suspended waveguides. Here we will report our progress in the electromagnetic modelling and simulation of sub-wavelength structures, providing at the same time an intuitive vision of their fundamental optical properties. Furthermore, we will address design strategies for several integrated optical devices based on these structures, and present the latest experimental results for structures operating both at near and mid-infrared wavelengths.

Détection et caractérisation de nouveaux disques circumstellaires autour d’étoiles de faibles masses et naines brunes jeunes.

La présence de disques circumstellaires signale la formation actuelle ou passée de systèmes planétaires, pour lesquels les processus de formation sont encore mal compris. Ce mémoire porte sur la détection et la caractérisation de disques circumstellaires autour d’étoiles de faibles masses (types spectraux > K5) et de naines brunes qui sont candidates ou membres d’associations cinématiques jeunes. Nous présentons ici les résultats de cette recherche ainsi que son implication pour la compréhension des processus de formation et d’évolution des systèmes planétaires. De l’échantillon initial composé de ∼ 1600 objets provenant des relevés BANYAN de Malo et al. ainsi que Gagné et al., dont seulement 600 satisfont nos critères de qualité sur les données, quatre nouveaux candidats de disque ont été découverts en détectant leur excès d’émission infrarouge dans les données d’archive de la mission WISE. Les données du relevé 2MASS ainsi que les spectres synthétiques BT-Settl ont été conjointement utilisés pour modéliser l’émission des étoiles. Les nouveaux candidats, dont les types spectraux sont tardifs (M4.5 à L0) et les masses se situent entre ∼ 13 et 120 M_Jup, ont des températures de disque de ∼ 135–520 K et des luminosités fractionnaires de 0,021–0,15. Pour deux des cibles, nous avons obtenu des spectres dans les longueurs d’onde visibles et infrarouges proches. Ces nouveaux spectres montrent respectivement des signes d’émission en Hα et Paβ, indiquant la présence d’accrétion, et ainsi de gaz, et renforçant l’hypothèse que ces objets sont réellement jeunes. Ces deux objets, vraisemblablement âgés de 40 Ma, pourraient représenter la première détection et caractérisation de disques porteurs de gaz plus vieux que 20 Ma.

Investigation of bonded hydrogen defects in nanocrystalline diamond films grown with nitrogen/methane/hydrogen plasma at high power conditions

In this work, we investigate the influence of some growth parameters such as high microwave power ranging from 3.0 to 4.0 kW and N2 additive on the incorporation of bonded hydrogen defects in nanocrystalline diamond (NCD) films grown through a small amount of pure N2 addition into conventional 4% CH4/H2 plasma using a 5 kW microwave plasma CVD system. Incorporation form and content of hydrogen point defects in the NCD films produced with pure N2 addition was analyzed by employing Fourier-transform infrared (FTIR) spectroscopy for the first time. A large amount of hydrogen related defects was detected in all the produced NCD films with N2 additive ranging from 29 to 87 µm thick with grain size from 47 nm to 31 nm. Furthermore, a specific new H related sharp absorption peak appears in all the NCD films grown with pure N2/CH4/H2 plasma at high powers and becomes stronger at powers higher than 3.0 kW and is even stronger than the 2920 cm−1 peak, which is commonly found in CVD diamond films. Based on these experimental findings, the role of high power and pure nitrogen addition on the growth of NCD films including hydrogen defect formation is analyzed and discussed.

Détection et caractérisation de nouveaux disques circumstellaires autour d’étoiles de faibles masses et naines brunes jeunes

La présence de disques circumstellaires signale la formation actuelle ou passée de systèmes planétaires, pour lesquels les processus de formation sont encore mal compris. Ce mémoire porte sur la détection et la caractérisation de disques circumstellaires autour d’étoiles de faibles masses (types spectraux > K5) et de naines brunes qui sont candidates ou membres d’associations cinématiques jeunes. Nous présentons ici les résultats de cette recherche ainsi que son implication pour la compréhension des processus de formation et d’évolution des systèmes planétaires. De l’échantillon initial composé de ∼ 1600 objets provenant des relevés BANYAN de Malo et al. ainsi que Gagné et al., dont seulement 600 satisfont nos critères de qualité sur les données, quatre nouveaux candidats de disque ont été découverts en détectant leur excès d’émission infrarouge dans les données d’archive de la mission WISE. Les données du relevé 2MASS ainsi que les spectres synthétiques BT-Settl ont été conjointement utilisés pour modéliser l’émission des étoiles. Les nouveaux candidats, dont les types spectraux sont tardifs (M4.5 à L0) et les masses se situent entre ∼ 13 et 120 M_Jup, ont des températures de disque de ∼ 135–520 K et des luminosités fractionnaires de 0,021–0,15. Pour deux des cibles, nous avons obtenu des spectres dans les longueurs d’onde visibles et infrarouges proches. Ces nouveaux spectres montrent respectivement des signes d’émission en Hα et Paβ, indiquant la présence d’accrétion, et ainsi de gaz, et renforçant l’hypothèse que ces objets sont réellement jeunes. Ces deux objets, vraisemblablement âgés de 40 Ma, pourraient représenter la première détection et caractérisation de disques porteurs de gaz plus vieux que 20 Ma.

Development and characterisation of solution processed vanadium oxide and transparent metal oxide thin films

Metal oxide thin films are important for modern electronic devices ranging from thin film transistors to photovoltaics and functional optical coatings. Solution processed techniques allow for thin films to be rapidly deposited over a range of surfaces without the extensive processing of comparative vapour or physical deposition methods. The production of thin films of vanadium oxide prepared through dip-coating was developed enabling a greater understanding of the thin film formation. Mechanisms of depositing improved large area uniform coverage on a number of technologically relevant substrates were examined. The fundamental mechanism for polymer-assisted deposition in improving thin film surface smoothness and long range order has been delivered. Different methods were employed for adapting the alkoxide based dip-coating technique to produce a variety of amorphous and crystalline vanadium oxide based thin films. Using a wide range of material, spectroscopic and optical measurement techniques the morphology, structure and optoelectronic properties of the thin films were studied. The formation of pinholes on the surface of the thin films, due to dewetting and spinodal effects, was inhibited using the polymer assisted deposition technique. Uniform thin films with sub 50 nm thicknesses were deposited on a variety of substrates controlled through alterations to the solvent-alkoxide dilution ratios and employing polymer assisted deposition techniques. The effects of polymer assisted deposition altered the crystallized VO thin films from a granular surface structure to a polycrystalline structure composed of high density small in-plane grains. The formation of transparent VO based thin film through Si and Na substrate mediated diffusion highlighted new methods for material formation and doping.

Cellular ROS imaging with hydro-Cy3 dye is strongly influenced by mitochondrial membrane potential

Background: Hydrocyanines are widely used as fluorogenic probes to monitor reactive oxygen species (ROS) generation in cells. Their brightness, stability to autoxidation and photobleaching, large signal change upon oxidation, pH independence and red/near infrared emission are particularly attractive for imaging ROS in live tissue. Methods: Using confocal fluorescence microscopy we have examined an interference of mitochondrial membrane potential (ΔΨm) with fluorescence intensity and localisation of a commercial hydro-Cy3 probe in respiring and non-respiring colon carcinoma HCT116 cells. Results: We found that the oxidised (fluorescent) form of hydro-Cy3 is highly homologous to the common ΔΨm-sensitive probe JC-1, which accumulates and aggregates only in ‘energised’ negatively charged mitochondrial matrix. Therefore, hydro-Cy3 oxidised by hydroxyl and superoxide radicals tends to accumulate in mitochondrial matrix, but dissipates and loses brightness as soon as ΔΨm is compromised. Experiments with mitochondrial inhibitor oligomycin and uncoupler FCCP, as well as a common ROS producer paraquat demonstrated that signals of the oxidised hydro-Cy3 probe rapidly and strongly decrease upon mitochondrial depolarisation, regardless of the rate of cellular ROS production. Conclusions: While analysing ROS-derived fluorescence of commercial hydrocyanine probes, an accurate control of ΔΨm is required. General significance: If not accounted for, non-specific effect of mitochondrial polarisation state on the behaviour of oxidised hydrocyanines can cause artefacts and data misinterpretation in ROS studies.

The spectral albedo of sea ice and salt crusts on the tropical ocean of Snowball Earth: II. Optical modeling

During the Snowball Earth events of the Neoproterozoic, tropical regions of the ocean could have developed a precipitated salt lag deposit left behind by sublimating sea ice. The major salt would have been hydrohalite, NaCl•2H2O. The crystals in such a deposit can be small and highly scattering, resulting in an allwave albedo similar to that of snow. The snow-free sea ice from which such a crust could develop has a lower albedo, around 0.5, so the development of a crust would substantially increase the albedo of tropical regions on Snowball Earth. Hydrohalite crystals are much less absorptive than ice in the near- infrared part of the solar spectrum, so their presence at the surface would increase the overall albedo as well as altering its spectral distribution. In this paper, we use laboratory measurements of the spectral albedo of a hydrohalite lag deposit, in combination with a radiative transfer model, to infer the inherent optical properties of hydrohalite as functions of wavelength. Using this result, we model mixtures of hydrohalite and ice representing both artificially created surfaces in the laboratory and surfaces relevant to Snowball Earth. The model is tested against sequences of laboratory measurements taken during the formation and the dissolution of a lag deposit of hydrohalite. We present a parameterization for the broadband albedo of cold, sublimating sea ice as it forms and evolves a hydrohalite crust, for use in climate models of Snowball Earth.

The optical properties of metamaterials

This thesis studies the parametric investigation, polarisation dependence and characterization of fishnet structure at near infrared wavelengths. Detailed simulations are performed to understand the behaviour of the structure at near infrared and optical wavelengths. Simulations are performed to obtain negative refractive index of the fishnet structure formed from nanoimprint lithography (NIL) by taking into account the effect of substrate and polymethyl methacrylate (PMMA) beneath it. Two different structures have been designed and fabricated of varying dimensions using NIL and their resonant wavelength measured in the near infrared at 1.45 µm and 1.88 µm. Simulations suggest that a negative refractive index real part with the magnitude -0.24 is found at 1.53 µm and this decrease to a maximum magnitude of -0.57 at 1.9 µm. The PMMA and suppressed pillars are here responsible for the increasing material losses and limiting the value of negative refractive index. An analytical approach has been suggested to characterise fishnet structures at oblique incidence. The expressions for an absorbing medium are rewritten for an alternative definition of refractive index. The expressions are initially validated for a dielectric slab and a metal film. These results provide the possibility that this proposal may yield a general algorithm for obtaining the complex reflection and transmission coefficients for artificial structures. FDTD simulations have been extensively used in this thesis to understand the optical metamaterials and their characterization.

Synthesis of novel organic semiconductors for optoelectronic devices

This thesis describes the synthesis and characterisation of novel conjugated organic materials with optoelectronic application. The first chapter provides an introduction about organic semiconductors and in particular about their working principle from a physical and chemical point of view. An overview of the most common types of solar cells is provided, including examples of some of the best performing materials. The second chapter describes the synthesis of a new library of flavin derivatives as potential active materials for optoelectronic applications. Flavins are natural redox-active molecules, which show potential application in optoelectronics, thanks to their stability and versatility. FPF-Flavins, for instance, could be used either as acceptor units in push-pull polyconjugated systems or as acceptor unit in dyes for DSSCs. In the same chapter a first attempt of synthesising bis-flavins to be used as N-type semiconductors in BHJ devices is described. The third chapter describes the successful synthesis and characterization of a series of conjugated organic molecules based on the benzothiadiazole moiety. Among these, three molecules containing ferrocene as donor unit were tested as sensitizers for DSSCs, reporting a PCE of 0.3% as the best result. Further studies indicated a significant problem of charge recombination which limits the performance. A near-infrared absorbing push-pull polymer, based on BbT as acceptor unit, was also synthesised and tested in BHJ devices as P-type semiconductor in blend with PC71BM, showing a VOC of 0.71 V. Finally, the last chapter describes the synthesis of several tetrathiafulvalene derivatives in order to explore this moiety as donor unit in dyes for DSSCs and as HTM for perovskite-based solar cells. In particular, two very simple dyes were synthesised and implemented in DSSCs reporting a PCE 0.2% and 0.4%, respectively. The low efficiency was associated to the tendency to aggregate at the solid state, with the absorption shifting from the visible to the infrared range. A conjugated molecule, containing a DPP core, was also synthesised and tested as HTM for perovskite solar cells. The best reported PCE of 7.7% was obtained without any additives. A case study about dehalogenation and “halogen dance” in TTF iodide is also presented.

Caracterização material e microbiológica de espécimes fotográficos

Neste trabalho foram estudadas quatro espécies fotográficas, dois ambrótipos do séc. XIX e dois negativos de gelatina do séc. XX. Estas espécies são suscetiveis a degradações, físicas, químicas e microbiológicas. Técnicas de análise não destrutivas como, a fotografia, a microscopia ótica, a microscopia eletrónica de varrimento e espetroscopia de raios-X por dispersão em energias, a micro-espetroscopia de infravermelho em modo de reflexão total atenuada, a micro-espetroscopia de Raman e a micro-difração de raios-X foram utilizadas na caracterização material. A colonização microbiológica das amostras foi estudada através do isolamento e caracterização dos microrganismos contaminantes. Foram ainda realizados estudos de determinação de atividade celulolítica para os isolados fúngicos provenientes dos ambrótipos bem como ensaios de simulação, nos quais se utilizaram estes isolados para induzir contaminação em ambrótipos contemporâneos e assim avaliar o seu potencial biodeteriogénico. Foi ainda avaliado o potencial biodeteriogénico de isolados bacterianos em negativos de gelatina contemporâneos; Abstract: Material and microbiological characterization of photographic specimens This work presents a scientific study of four photographic specimens, two ambrotypes and two gelatin-silver negative plates from 19th and 20th century, respectively. These specimens are susceptible to physical, chemical and microbiological degradations. A non-destructive approach was used based on techniques such as technical photography, optical microscopy, scanning electron microscopy, infrared micro-spectroscopy, micro-Raman spectroscopy and X-rays micro-diffraction. Microbiological colonization of the samples was studied by isolation and characterization of the contaminating microorganisms. Studies to evaluate cellulolytic activity of fungal isolates from the ambrotypes were carried out and also simulation assays in which were used these isolated to induce contamination in contemporary ambrotypes were done to evaluate their biodeteriogenic potential. It was also studied the biodeteriogenic potential of the bacterial isolates from gelatin-silver negative plates which were subsequently inoculated in contemporary gelatin-silver negatives.

Development of new immunochemical and spectroscopic analytical methods for the characterization and conservation of works of art

Cultural heritage is constituted by complex and heterogenous materials, such as paintings but also ancient remains. However, all ancient materials are exposed to external environment and their interaction produces different changes due to chemical, physical and biological phenomena. The organic fraction, especially the proteinaceous one, has a crucial role in all these materials: in archaeology proteins reveal human habits, in artworks they disclose technics and help for a correct restoration. For these reasons the development of methods that allow the preservation of the sample as much as possible and a deeper knowledge of the deterioration processes is fundamental. The research activities presented in this PhD thesis have been focused on the development of new immunochemical and spectroscopic approaches in order to detect and identify organic substances in artistic and archaeological samples. Organic components could be present in different cultural heritage materials as constituent element (e.g., binders in paintings, collagen in bones) and their knowledge is fundamental for a complete understanding of past life, degradation processes and appropriate restauration approaches. The combination of immunological approach with a chemiluminescence detection and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry allowed a sensitive and selective localization of collagen and elements in ancient bones and teeth. Near-infrared spectrometer and hyper spectral imaging have been applied in combination with chemometric data analysis as non-destructive methods for bones prescreening for the localization of collagen. Moreover, an investigation of amino acids in enamel has been proposed, in order to clarify teeth biomolecules survival overtime through the optimization and application of High-Performance Liquid Chromatography on modern and ancient enamel powder. New portable biosensors were developed for ovalbumin identification in paintings, thanks to the combination between biocompatible Gellan gel and electro-immunochemical sensors, to extract and identify painting binders with the contact only between gel and painting and between gel and electrodes.

Design and characterization of automated agricultural vehicle systems

Nowadays, technological advancements have brought industry and research towards the automation of various processes. Automation brings a reduction in costs and an improvement in product quality. For this reason, companies are pushing research to investigate new technologies. The agriculture industry has always looked towards automating various processes, from product processing to storage. In the last years, the automation of harvest and cultivation phases also has become attractive, pushed by the advancement of autonomous driving. Nevertheless, ADAS systems are not enough. Merging different technologies will be the solution to obtain total automation of agriculture processes. For example, sensors that estimate products' physical and chemical properties can be used to evaluate the maturation level of fruit. Therefore, the fusion of these technologies has a key role in industrial process automation. In this dissertation, ADAS systems and sensors for precision agriculture will be both treated. Several measurement procedures for characterizing commercial 3D LiDARs will be proposed and tested to cope with the growing need for comparison tools. Axial errors and transversal errors have been investigated. Moreover, a measurement method and setup for evaluating the fog effect on 3D LiDARs will be proposed. Each presented measurement procedure has been tested. The obtained results highlight the versatility and the goodness of the proposed approaches. Regarding the precision agriculture sensors, a measurement approach for the Moisture Content and density estimation of crop directly on the field is presented. The approach regards the employment of a Near Infrared spectrometer jointly with Partial Least Square statistical analysis. The approach and the model will be described together with a first laboratory prototype used to evaluate the NIRS approach. Finally, a prototype for on the field analysis is realized and tested. The test results are promising, evidencing that the proposed approach is suitable for Moisture Content and density estimation.