Vidros dopados com íons terras-raras trivalentes TR3+, são materiais importantes devido a suas potenciais aplicações tecnológicas como em dispositivos luminescentes e lasers de estado sólido. Os TR3+ possuem níveis de energia eletrônicos que permitem obter emissões desde o ultravioleta até o infravermelho próximo. A classe de vidros tungstênio fosfatos tem sido amplamente estudada devido as suas propriedades incomuns aos vidros fosfato clássicos como, por exemplo, alta estabilidade térmica contra devitrificarão, absorção óptica não linear e efeitos fotocrômicos mediante irradiação. Neste trabalho, foram estudados vidros tungstênio fosfato dopados com os íons Nd3+, Tb3+ e co-dopados com os íons Er3+ e Yb3+, no sistema composicional 90NaPO3-10WO3 + x%Nd2O3 (x = 0,25; 0,5; 1; 3 e 5% em peso em excesso) 90NaPO3 – 10WO3 + y%TbF3 (y = 0,1; 0,5; 1; 3 e 5 em peso em excesso) (90-z-k)NaPO3 – 10WO3 + z%Er2O3 + k%Yb2O3 (z = 0,25; 0,5; e 1 mol%; k = 0 e 2 mol%). As amostras foram obtidas pelo método convencional de fusão e resfriamento e foram caracterizadas por absorção UV-VIS-NIR, fotoluminescência (emissão e excitação), e tempos de vida de estado excitado. Para as amostras dopadas com Nd3+ foram observadas emissões intensas em 1060 nm, os tempos de vida do nível emissor 4F3/2 foram medidos e a eficiência quântica do sistema foi estimada. As amostras dopadas com Tb3+ apresentaram o pico de emissão de maior intensidade em 542 nm, porém para os vidros com baixa concentração de íon dopante, duas transições com intensidades relativas da mesma ordem da transição do verde, correspondentes a emissões em 415 nm e 435 nm, foram observadas e o tempo de vida para estado emissor 5D4 também foi medido. Os vidros co-dopados com Er3+/Yb3+ apresentaram emissões intensas em 522 nm, 545 nm e 658 nm em um processo de conversão ascendente de energia (upconversion) que envolve dois fótons. Os tempos de vida do estado emissor 4I13/2 do Er3+ dessa amostra também foram mensurados. / Glasses and glass-ceramics doped with trivalent earth-rare ions TR3+, are important materials due to their potential technological applications, such as in luminescent devices and solid-state lasers. These ions have electronic energy levels that allow emissions from ultraviolet to infrared. The tungsten phosphate glass class has been extensively studied due to its unusual properties when compared to the classical phosphate glasses, such as high thermal stability against devitrification, nonlinear optical absorption, photochromic effects under visible irradiation, and efficient emission properties of earth-rare ions. In this work, tungsten phosphate glasses doped with Nd3+ and Tb3+ ions. and co-doped with Er3+ and Yb3+ ions, were studied in the compositional system 90NaPO3-10WO3 + x%Nd2O3 (x = 0.25; 0.5; 1; 3 e 5% by weight in excess) 90NaPO3 – 10WO3 + y%TbF3 (y = 0.1; 0.5; 1; 3 e 5 by weight in excess) (90-z-k)NaPO3 – 10WO3 + z%Er2O3 + k%Yb2O3 (z = 0.25; 0.5; e 1 mol%; k = 0 e 2 mol%). The samples were obtained by the conventional melt quenching technique and were characterized by UV-VIS-NIR absorption, photoluminescence (emission and excitation), and excited state lifetime values. For samples doped with Nd3+ intense emissions were observed at 1060 nm, the lifetimes of the 4F3/2 emitting level were measured and the quantum efficiency of the system was estimated. The Tb3+ doped samples presented the highest intensity emission peak at 542 nm, but for the glasses with low dopant ion concentration, two transitions with relative intensities of the same order of the green transition, corresponding to emissions at 415 nm and 435 nm were detected. The lifetime value of the 5D4 emitting state was also measured. The Er3+/Yb3+ co-doped glasses exhibited intense emission at 522 nm, 545 nm and 658 nm in an upconversion process involving two photons, the lifetime of the emitting state 4I13/2 of Er3+ were also measured for these samples.

This thesis comprises of essentially two parts. The first deals with materials in a fusion reactor and examines how neutron damage affects material in a fusion reactor, with focus on how this is important for plasma damage. The methods used are neutron transport, primary event analysis and molecular dynamics. It found that the neutron damage by 14 MeV neutrons is restricted to back scatter events within the surface (first 20 microns). Molecular dynamics analysis showed that the issue of cascades is heavily dependent on direction of primary event and the energy of such. Statistical analysis was done to provide a standard approach for modelling of damage through neutrons. The second deals with the relaxation of magnetic flux ropes with an emphasis on kink unstable flux ropes. A relaxation model was developed which shows good approximation to simulation results of merging magnetic flux ropes. Subsequently, work was done to establish the physical processes involved in relaxation. This was done by examining magnetohydrodynamic (MHD) simulations of two flux ropes, one unstable and one stable. It was found that there is is a clear distance at which merger does not occur any more. Furthermore, a critical current seems to be a requirement at the edge a stable flux rope.

Made available in DSpace on 2016-12-23T14:08:14Z (GMT). No. of bitstreams: 1 Capa, Cap 1 e Cap 2 ate secao 2-2-1-9.pdf: 1005078 bytes, checksum: 68579a03ea37b6d408ea44008ec9ad0f (MD5) Previous issue date: 2010-12-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho tem o objetivo de avaliar uma possível relação entre as propriedades mecânicas calculadas a partir dos dados de micropenetração instrumentada e o comportamento sob desgaste microabrasivo dos compósitos à base de tungstênio (W) infiltrados por latão, usados em coroas diamantadas utilizadas em sondagem mineral. As amostras dos compósitos de tungstênio foram sinterizadas com combinações de diferentes tamanhos de partículas W e adições de ligas à base de outros elementos, além de adições de abrasivos secundários (SiC). Após a preparação metalográfica, as amostras foram analisadas em um micropenetrador instrumentado com um pen etrador do tipo Vickers. As fases foram penetradas com uma carga de 30 mN, exceto o carbeto de silício, com carga de 250 mN. As curvas geradas a cada penetração permitiram calcular a microdureza e o módulo de elasticidade para cada fase. Estes resultados foram comparados com os coeficientes de desgaste microabrasivo dimensionais obtidos em um trabalho anterior, através de ensaios de microabrasão com lamas abrasivas à base de carbeto de silício, sílica e hematita, efetuados com equipamento do tipo Calowear. Foi observada uma diminuição na microdureza conforme o tamanho dos grãos de tungstênio aumenta. Para a lama abrasiva contendo SiC, uma diminuição no coeficiente de desgaste microabrasivo se seguiu à diminuição na microdureza do tungstênio. O oposto foi observado com a lama de SiO2, enquanto, para a lama de Fe2O3, nenhuma correlação clara foi obtida. Também é importante dizer que o efeito da dureza do latão infiltrado (fase aglutinante) tornou-se mais significativa nos ensaios com as pastas de SiO2 e de Fe2O3. Quando as ligas à base de outros elementos são adicionadas, para o abrasivo SiC, o aumento da plasticidade do latão aumenta o desgaste, porque as deformações plásticas são aumentadas, levando em consideração a relação Habr./Hfase muito alta. A plasticidade da fase W parece não interferir no desgaste. Ocorre o contrário para o abrasivo SiO2. Para ambos os abrasivos, o cobre adicionado aumenta a fração volumétrica de fase macia , proporcionando um desgaste ainda maior. Para o abrasivo Fe2O3, o aumento na plasticidade do latão aumenta o coeficiente de desgaste, pois leva a indentações maiores, ou seja, a maiores deformações plásticas. Dependendo do tipo do abrasivo, os mecanismos observados foram riscamento e rolamento de partículas (múltiplas indentações), além da ocorrência de ambos simultaneamente, embora dissociados / This work intends to evaluate a possible relationship between the mechanical properties calculated from instrumented microindentation data and the microabrasive wear behavior of infiltrated tungsten (W) composites used in impregnated diamond bits for rock drilling. Specimens of brass-infiltrated W composites were sintered with combinations of different W particle sizes, and additions of alloys based on other elements, as well as additions of secondary abrasives. After metallographic preparation, the specimens were analyzed in an instrumented microindenter with a Vickers indenter. All phases were indented with a load of 30 mN, except the silicon carbide, with a load of 250 mN. The indentation curves allowed the calculation of microhardness and Young s modulus for each phase. Those results were compared with dimensional microabrasive wear coefficients obtained in a previous work, by testing microabrasion with abrasive slurries based on silicon carbide, silica and hematite, performed with Calower equipment. It was observed a decrease in microhardness as the tungsten grains size increase. For the SiC abrasive slurry, a decrease in microabrasive wear coefficient followed the decrease in tungsten microhardness. The opposite was observed with the SiO2 slurry, whereas, for the Fe2O3 slurry, no clear correlation was obtained. It is also important to say that the effect of infiltrated brass (binder phase) hardness became more significant in the tests with the SiO2 and Fe2O3 slurries. When the alloys based on other elements are added, to the SiC abrasive, the increase of the brass plasticity increases its wear, because the plastic deformations are increased, taking into account the very high Habr./Hphase relation. The plasticity of the W phase seems not to interfere in wear. The opposite is true for the SiO2 abrasive. For both abrasives, the copper added increases the "soft" phase volumetrical fraction, providing an additional wear. For the Fe2O3 abrasive, the increase in the brass plasticity increases the wear coefficient, since it leads to larger indentations, i. e., to larger plastic deformations. Depending on the abrasive type, the observed mechanisms were grooving and particles rolling (multiple indentations), besides the occurrence of both simultaneously, although, dissociated

Weld joint penetration determination is the key factor in welding process control area. Not only has it directly affected the weld joint mechanical properties, like fatigue for example. It also requires much of human intelligence, which either complex modeling or rich of welding experience. Therefore, weld penetration status identification has become the obstacle for intelligent welding system. In this dissertation, an innovative method has been proposed to detect the weld joint penetration status using machine-learning algorithms. A GTAW welding system is firstly built. Project a dot-structured laser pattern onto the weld pool surface during welding process, the reflected laser pattern is captured which contains all the information about the penetration status. An experienced welder is able to determine weld penetration status just based on the reflected laser pattern. However, it is difficult to characterize the images to extract key information that used to determine penetration status. To overcome the challenges in finding right features and accurately processing images to extract key features using conventional machine vision algorithms, we propose using convolutional neural network (CNN) to automatically extract key features and determine penetration status. Data-label pairs are needed to train a CNN. Therefore, an image acquiring system is designed to collect reflected laser pattern and the image of work-piece backside. Data augmentation is performed to enlarge the training data size, which resulting in 270,000 training data, 45,000 validation data and 45,000 test data. A six-layer convolutional neural network (CNN) has been designed and trained using a revised mini-batch gradient descent optimizer. Final test accuracy is 90.7% and using a voting mechanism based on three consequent images further improve the prediction accuracy.

<p>Ceramics constitute an important group of low-density armour materials. Their high intrinsic strength makes it possible to design ceramic armour systems capable of defeating projectiles directly on the ceramic surface. This capability, named interface defeat, signifies that the projectile material is forced to flow radially outwards on the surface of the ceramic without penetrating significantly.</p><p>This thesis presents impact experiments between long-rod projectiles and ceramic targets. The projectile/target interaction was studied using flash X-ray technique. Transition velocities (the impact velocity at which interface defeat can no longer be maintained and penetration starts) were estimated for different combinations of metallic projectiles and ceramic targets and compared to critical velocities estimated on a theoretical basis. Replica scaling experiments were also performed in order to investigate the possible influence of scale.</p><p>All ceramic materials tested showed a distinct transition from interface defeat to penetration. Experiments with different silicon carbides showed that the transition velocity correlated better with the fracture toughness than with the hardness of the ceramic materials. For conical projectiles, penetration occurred along a conical surface crack and at a lower transition velocity than that observed for cylindrical projectiles. Experiments with unconfined alumina targets in different scales showed only a slight increase in dimensionless final penetration with length scale.</p><p>A unique transition velocity seems to exist for each combination of projectile, target material and target configuration. This velocity was found to depend on both the strength (hardness) and the brittleness (fracture toughness) of the ceramic. The lower transition velocity of conical projectiles compared with cylindrical ones is mainly due to the radially expanding load and the penetration of projectile material into surface cracks. The results of the experiments in different scales indicate that replica scaling is valid for penetration in ceramics.</p>

Ceramics constitute an important group of low-density armour materials. Their high intrinsic strength makes it possible to design ceramic armour systems capable of defeating projectiles directly on the ceramic surface. This capability, named interface defeat, signifies that the projectile material is forced to flow radially outwards on the surface of the ceramic without penetrating significantly. This thesis presents impact experiments between long-rod projectiles and ceramic targets. The projectile/target interaction was studied using flash X-ray technique. Transition velocities (the impact velocity at which interface defeat can no longer be maintained and penetration starts) were estimated for different combinations of metallic projectiles and ceramic targets and compared to critical velocities estimated on a theoretical basis. Replica scaling experiments were also performed in order to investigate the possible influence of scale. All ceramic materials tested showed a distinct transition from interface defeat to penetration. Experiments with different silicon carbides showed that the transition velocity correlated better with the fracture toughness than with the hardness of the ceramic materials. For conical projectiles, penetration occurred along a conical surface crack and at a lower transition velocity than that observed for cylindrical projectiles. Experiments with unconfined alumina targets in different scales showed only a slight increase in dimensionless final penetration with length scale. A unique transition velocity seems to exist for each combination of projectile, target material and target configuration. This velocity was found to depend on both the strength (hardness) and the brittleness (fracture toughness) of the ceramic. The lower transition velocity of conical projectiles compared with cylindrical ones is mainly due to the radially expanding load and the penetration of projectile material into surface cracks. The results of the experiments in different scales indicate that replica scaling is valid for penetration in ceramics.

Reservoir-type dispenser hollow cathodes are currently being developed for use on NASAs Prometheus 1 mission. In these cathodes, the reaction between a barium source material and tungsten powder contained in a cavity surrounding a porous tungsten emitter produces barium vapor which is crucial to operation of the cathode. The primary objective of this research was to investigate the reactions between tungsten and a commercial barium source material in a simulated reservoir hollow cath-ode environment. Mixtures of tungsten and a barium calcium aluminate material were sealed inside molybdenum capsules with porous tungsten closures and heated to 1000?1200?and 1300?or 100, 200, and 400 hours. Based on the reaction products, which were identified to be BaAl2O4 and Ba2CaWO6, a reaction was proposed for the barium calcium aluminate material with tungsten. The bottom pellets in the capsules were found to have reacted to a much further extent than the top pellets in all of the samples, possibly due to a temperature gradient or excessive moisture in the base of the capsules. Quantita-tive and semi-quantitative x-ray analysis results did not show a clear trend as to how the concentrations of BaAl2O4 and Ba2CaWO6 vary with time. Most of the barium source materials are hygroscopic, and hydration of the materi-als would substantially reduce the performance of the cathode. Therefore, the environ-mental stability of several barium compounds, 3BaO??2O3 (B3A), 6BaO????2O3 (612), 4BaO????O3 (411), Ba2.9Ca1.1Al2O7 (B4ASSL), and Ba3Sc4O9, were investi-gated in order to evaluate their suitability for use as barium source materials. A micro-balance was used to measure weight gain of the materials as they were exposed to dew points of ??C and 11?t room temperature. The results showed that B3A hydrated more extensively than any of the other materials tested in the low- and intermediate-humidity environments, while the 612, 411, and B4ASSL materials were all reasonably stable in the low-humidity environment. The Ba3Sc4O9 was extremely stable compared to the barium aluminates in the intermediate-humidity conditions.

Silver is a precious metal having antibacterial property and widely used in industry mostly for water purification and medicinal products. Therefore, the determination of trace levels of silver is important for industrial applications. Flame atomic absorption spectrometry (FAAS) is a popular technique for the determination of relatively low concentration levels. This mature technique owes its widespread application to its simplicity and low cost. However, for some occasions, FAAS technique suffers from its low sensitivity because of low nebulization efficiency and relatively short residence time of analyte atoms in the measurement zone. In order to overcome this sensitivity problem, atom traps have been developed in recent years. Slotted quartz tube (SQT) is an accessory designed to use as an atom trap in conventional flame atomic absorption burner head. This thesis study involves the development of a sensitive, simple and economical technique with the help of the SQT for the determination silver. Firstly, the technique known as SQT-FAAS was used to increase the residence time of analyte atoms in the measurement zone. In this case, limit of detection (LOD) and characteristic concentration (C0) values were found to be 19 ng/mL and 35 ng/mL, respectively. Enhancement in sensitivity with respect to FAAS was found to be 2.31 fold using SQT-FAAS. Regarding the angle between the two slots of the SQT, 180&deg / configuration was used. Secondly, in order to improve sensitivity further, the SQT was used as an atom trap (AT) where the analyte is accumulated in its inner wall prior to re-atomization. The signal is formed after reatomization of analyte atoms on the trap surface by introduction of organic solvent. For this purpose, uncoated SQT was used as a trap medium. However, there was a memory effect. Therefore, the SQT inner surface was coated with different coating elements and theoptimum conditions were found by using W-coated SQT-AT-FAAS technique. In the presence of a lean air-acetylene flame, analyte atoms were trapped in the inner surface of the SQT for 5.0 min and then revolatilized with the introduction of 25 &mu / L isobutyl methyl ketone (IBMK) / afterwards, a transient signal was obtained. These optimized parameters were used for uncoated SQT, W-coated SQT and Zr-coated SQT atom trap techniques. Sample suction rate was 6.25 mL/min in all techniques. Sensitivity was increased 54 fold using uncoated SQT-AT-FAAS technique with respect to simple FAAS technique. When W-coated SQT-AT-FAAS technique was applied, 135 fold sensitivity enhancement was obtained with respect to FAAS technique. The best sensitivity enhancement, 270 fold, was obtained using Zr-coated SQT-AT-FAAS technique. In addition, the Ag signals were more reproducible (%RSD, 1.21) when Zr was used as a coating element. After the sensitive technique was developed, interference effects of some transition and noble metals and hydride forming elements on Ag signals were investigated. Finally, surface studies were done to determine the chemical state of Ag during trapping period by using X-ray Photoelectron Spectroscopy (XPS). It was observed that the Ag analyte is retained on the SQT surface in its oxide form.

<p>The major part of the present work, deals with the reduction kinetics of Cu₂O powder and a Cu₂O-WO₃ powder mixture by hydrogen gas, studied by ThermoGravimetric Analysis (TGA). The reduction experiments were carried out both isothermally and non-isothermally on thin powder beds over different temperature intervals. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The activation energy for the reactions was evaluated from isothermal as well as non-isothermal reduction experiments.</p><p>In the case of the reduction of Cu₂O, the impact of the stability of the copper oxide on the activation energy for hydrogen reduction under identical experimental conditions is discussed. A closer investigation of additions of Ni or NiO to Cu₂O did not have a perceptible effect on the kinetics of reduction.</p><p>In the case of the reduction of the Cu₂O-WO₃mixture, the reaction mechanism was found to be affected in the temperature range 923-973 K, which is attributed to the reaction/transformation in the starting oxide mixture. At lower temperatures, Cu₂O was found to be preferentially reduced in the early stages, followed by the reduction of the tungsten oxide. At higher temperatures, the reduction kinetics was strongly affected by the formation of a complex oxide from the starting materials. It was found that the Cu₂O-WO₃mixture underwent a reaction/transformation which could explain the observed kinetic behavior.</p><p>The composition and microstructures of both the starting material and the reaction products were analyzed by X-ray diffraction (XRD) as well as by microprobe analysis. vi Kinetic studies of reduction indicated that, the mechanism changes significantly at 923 K and the product formed had unusual properties. The structural studies performed by XRD indicated that, at 923 K, Cu dissolved in W forming a metastable solid solution, in amorphous/nanocrystalline state. The samples produced at higher as well as lower temperatures, on the other hand, showed the presence two phases, pure W and pure Cu. The SEM results were in conformity with the XRD analysis and confirmed the formation of W/Cu alloy. TEM analysis results confirmed the above observations and showed that the particle sizes was about 20 nm.</p><p>The structure of the W/Cu alloy produced in the present work was compared with those for pure copper produced from Cu2O produced by hydrogen reduction under similar conditions. It indicated that the presence of W hinders the coalescence of Cu particles and the alloy retains its nano-grain structure. The present results open up an interesting process route towards the production of intermetallic phases and composite materials under optimized conditions.</p>

There has been an increase in the interest in fluoride materials over the last decade. This interest has focused on multiferroic materials and kagome lattices, to name but a few areas. This thesis focuses on the synthesis and crystallographic characterisation of selected transition metal fluorides and oxyfluorides. Work is presented on the tetragonal tungsten bronze solid solutions of KₓFeF₃, where x = 0.58 and x ≈ 0.5, and the copper analogue, K₃Cu₃Fe₂F₁₅; the kagome structure of Cs₂ZrCu₃F₁₂; and hydrothermal reactions using vanadium, manganese, or molybdenum as the transition metals in the formation of new fluorides and oxyfluorides. The tetragonal tungsten bronze compounds KₓFeF₃ (x = 0.58 and x ≈ 0.5) are both tetragonal at 500 K. In the variant with the lower K-content, there is a clear phase separation into two tetragonal phases even at this temperature. The K₀.₅₈FeF₃ sample separates into two distinct phases below 340 K to possess one tetragonal and one orthorhombic phase. Then at roughly 300 K, both samples undergo a phase transition where the tetragonal phase in the P4/mbm space group in K₀.₅₈FeF₃ changes to an orthorhombic phase with a larger unit cell; and the tetragonal phase in P4₂bc for the K₀.₅FeF₃ sample changes to the same orthorhombic model, whilst the P4/mbm model remains unchanged. The evolution of the lattice parameters and phase fractions is studied in detail using synchrotron powder X-ray diffraction (sPXRD). The kagome structure investigated, Cs₂ZrCu₃F₁₂, possesses the “ideal” kagome lattice at room temperature, but previous work has suggested that there is a phase transition at 225 K. The two structures are determined by single crystal X-ray diffraction at 300 K and 125 K. Variable temperature sPXRD studies are performed between these two temperature ranges to determine the phase evolution as a function of temperature. The structure changes from a rhombohedral to a monoclinic phase at low temperature. This is the result of the buckling of the kagome layers at the phase transition. The Zr⁴⁺ ion changes from 6 to 7 coordinate and this is seen as the main driving force for the distortion of the kagome layer from its “ideal” planar arrangement. ii The phase transition is first-order as seen from the electrical impedance measurements. The hydrothermal reactions presented reveal seven new materials and their crystal structures. Sr₂V₂F₁₀·H₂O is new and found to be isostructural to Sr₂Fe₂F₁₀·H₂O. BaVO₂F₃ is a cubic material that is potentially piezoelectric. Two hybrid organic inorganic manganese compounds are reported. The ladder structure (C₃N₂H₅)[Mn₂F₆(H₂O)₂] crystallises in a polar space group and shows promise as a candidate for multiferroic studies. The second hybrid material, (C₇NH₁₆)₂[MnF₅(H₂O)]·2H₂O, crystallises in a centrosymmetric space group. The Mo hybrid materials are all centrosymmetric and possess isolated molybdenum-centred monomeric or dimeric octahedral units.