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Made available in DSpace on 2014-10-09T12:26:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:39Z (GMT). No. of bitstreams: 0 / Neste trabalho, foi investigada a influência de alguns agentes controladores de processo (ACP), a saber: ácido esteárico, etanol, metanol e ciclohexano, na ativação mecânica de misturas de pós de 25% at. de nióbio e 75% at. de alumínio (correspondente à estequiometria do composto intermetálico NbAl3), com posterior reação de combustão. Os agentes foram adicionados à mistura em questão com o intuito de estabelecer um equilíbrio entre os eventos de soldagem e fratura durante o processamento em moinho de alta energia SPEX® 8000. A influência das variáveis (tipo e quantidade) relativas aos ACPs na densidade relativa das pastilhas reagidas de NbAl3 foram avaliadas mediante a elaboração de planejamentos de experimentos, do tipo composto central para dois fatores, para cada agente. Foi possível construir modelos empíricos para os ACPs ácido esteárico, metanol e ciclohexano, capazes de relacionar numericamente as variáveis (tempo de moagem e quantidade de ACP) investigadas em cada planejamento e indicar a melhor condição para se obter a otimização da resposta avaliada. Os resultados das análises de distribuição granulométrica e a caracterização microestrutural por microscopia eletrônica de varredura permitiram avaliar os efeitos dos agentes na distribuição do tamanho de partículas e na formação dos agregados de Nb/Al. A influência dos ACPs na evolução da reação de combustão foi avaliada mediante a análise das temperaturas de ignição registradas durante o processo. A espectroscopia no infravermelho possibilitou sugerir um mecanismo para a atuação do ácido esteárico e dos álcoois (etanol e metanol) com os pós metálicos durante a moagem. Constatou-se que os agentes afetam de forma significativa o processo de ativação mecânica, resultando em diferentes resultados de densidade relativa. Essa influência depende do tempo de moagem adotado. Os efeitos mais pronunciados na cinética de moagem e as maiores densidades relativas para o NbAl3 foram obtidos com o uso dos agentes ácido esteárico e etanol. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2017-09-27T19:14:47Z No. of bitstreams: 2 Dissertação - Leonardo S. Oliveira.pdf: 12252504 bytes, checksum: 0e50a939b3de4c6ee29549c3e7da914c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2017-09-27T19:15:01Z (GMT) No. of bitstreams: 2 Dissertação - Leonardo S. Oliveira.pdf: 12252504 bytes, checksum: 0e50a939b3de4c6ee29549c3e7da914c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-09-27T19:15:01Z (GMT). No. of bitstreams: 2 Dissertação - Leonardo S. Oliveira.pdf: 12252504 bytes, checksum: 0e50a939b3de4c6ee29549c3e7da914c (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-08-07 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A blend of elemental powders of Ni, Ti, Ge in the nominal composition Ni33Ti33Ge34 was subjected to mechanical alloying for 84h20min. The evolution of its structural and thermal characteristics was investigated by X-ray diffraction (XRD), Rietveld method (RM) and differential scanning calorimetry (DSC). Indeed, the inclusion of defects caused by milling induced a number of structural changes. I just five minutes of synthesis, it was ascertained the nucleation of intermetallics with crystallites sizes in nanometric dimensions. The formation of multiple phases is assigned to the low formation energy of the formed compound, among them the ternary alloy NiTiGe of the space group Pnma. From 2h20min, the crystalline structures undergo a remarkable degree of amorphization, reaching its maximum in 34h20min. Subsequently, in 59h20min, the metastability of the amorphous component gives rise to the re-nucleation of NiGe and Ni2.74Ge2 phases, which minimizing its free energy. In addition to this, the mechanical crystallization led to the formation of the TiO2-II high pressure phase and the B19’-NiTi shape memory alloy. In sequence, the amorphous content grows again and, with the growth of the tetragonal TiO2 phase, in 84h20min, the system recrystallizes and the milling was stopped. Therefore, it is observed that the system under study experiences a succession of metastable equilibrium due to the milling. / Uma mistura de pós elementares de Ni, Ge e Ti na composição nominal Ni33Ti33Ge34 foi submetida a mechanical alloying (MA) por 84h20min. A evolução das suas características estruturais e térmicas foram investigadas por difração de raios-X (DRX), método de Rietveld (MR) e calorimetria diferencial de varredura (DSC). De fato, a inclusão de defeitos provocados pela moagem induziu uma série de modificações estruturais. Em apenas cinco minutos de síntese, foi observada a nucleação de intermetálicos com cristalitos de dimensões nanométricas. A formação de múltiplas fases é atribuída a baixas energia de formação dos compostos formados, dentre elas a liga ternária NiTiGe do grupo espacial Pnma. A partir de 2h20min, as estruturas cristalinas presentes sofrem um notável grau de amorfização, atingindo seu máximo em 34h20min. Posteriormente, em 59h20min, a metaestabilidade da componente amorfa dá origem a re-nucleação das fases NiGe e Ni2.74Ge2, minimizando sua energia livre. Além dessas, a cristalização mecânica conduziu a cristalização da fase de alta pressão TiO2-II e da liga de memória de forma B19’-NiTi. Na sequência, a fração amorfa volta a crescer e, com a cristalização da fase TiO2 tetragonal em 84h20min, sistema recristaliza e a moagem foi interrompida. Dessa forma, nota-se que o sistema em estudo sofre uma sucessão de equilíbrios metaestáveis em função da moagem.

Neste trabalho, investigou-se a elaboração mecânica do composto intermetálico TiFe por moagem de bolas com alta energia. Uma forte aderência do material moído, particularmente nas paredes do recipiente de moagem, foi o principal problema verificado com tempos de moagem superiores a 1 hora (moinho agitador). Tentativas para resolver este problema foram realizadas inicialmente com o emprego de agentes controladores de processo (ACPs), como etanol, ácido esteárico, polietileno de baixa densidade, benzeno e ciclohexano, em diferentes quantidades (1 a 20% em massa) e tempos (1 a 40 h), mantendo-se constantes outros parâmetros de moagem como a razão bola:pó em massa (10:1) e o tamanho das bolas (=7mm). Os rendimentos mais elevados (em termos da massa de pó não aderido) foram obtidos quando se utilizaram grandes quantidades de benzeno e ciclohexano (101 e 103% em massa, respectivamente), porém com a formação de TiC ao invés de TiFe em razão da decomposição do ACP e reação do carbono com as partículas de titânio. As moagens foram realizadas posteriormente sem o emprego de qualquer ACP e também utilizando um moinho planetário. Várias estratégias foram investigadas para se tentar mitigar a aderência incluindo-se: (a) moagem de uma pequena quantidade da mistura de pós de Ti e de Fe, revestindo as paredes do recipiente e as bolas de moagem, antes da moagem da carga principal, (b) moagem pausada com aberturas intermediarias do recipiente em atmosfera ambiente, (c) moagem pausada para rotação e inversão da posição do recipiente de moagem (apenas no moinho agitador), (d) moagem isolada dos pós de Ti e de Fe, antes da moagem da mistura, e (e) moagem do pó de Fe com o Ti hidretado. Os melhores resultados, em termos de diminuição da aderência combinada com a formação majoritária do composto TiFe durante a moagem, foram obtidos quando se adotou o procedimento de inversão/rotação, juntamente com o processo de revestimento preliminar do recipiente e das bolas de moagem (26% em massa). Rendimentos maiores foram obtidos com a utilização do TiH2 no moinho planetário, porém sem a formação majoritária do TiFe durante a moagem. / In this work an investigation on the mechanical alloying of the intermetallic compound TiFe by high-energy ball milling was conducted. Strong adherence of milled material, particularly at the vial walls, was seen to be the main problem at milling times higher than 1 hour (shaker mill), hindering the compound synthesis. Attempts to prevent this problem were accomplished first by adding different process control agents (PCAs), like ethanol, stearic acid, low density polyethylene, benzene and cyclohexane at variable quantities (1 to 20 wt. %) and times (1 to 40 h), keeping constant other milling parameters like ball to powder mass ratio (10:1) and balls size (=7mm). Highest yields (related to the non adhered powder) were attained with larger amounts of benzene and cyclohexane (101 and 103 wt. %, respectively), but with TiC formation during milling instead of TiFe due to the PCA decomposition and the reaction of the carbon with and titanium particles. Milling was conducted further without adding any PCA and also using a planetary ball mill. Several strategies were tried to avoid or minimize the adherence including: (a) milling of a small quantity of the Ti and Fe powder mixture, dirtying the vial walls and the balls surfaces before milling the main charge, (b) stepwise milling with intermediate openings of the vial in air, (c) stepwise milling with the rotation and the inversion of the vial position between the steps (only in the shaker mill), (d) milling Ti and Fe powders (apart from each other) before milling the mixture of them, and (e) milling Fe powder with Ti hydride powder. Best results concerning both yield and major TiFe formation during milling were verified with the rotation/inversion procedure combined with preliminar dirtying of the vial and balls (26 wt.% in the shaker mill). Higher yields could be attained by using TiH2 powder in the planetary mill, but with no major TiFe formation during milling.

Les alliages Fe-Si sont connus pour combiner d’excellentes propriétés magnétiques avec de bonnes propriétés électriques (forte résistivité électrique). Dans ce contexte nous avons recherché à élaborer des matériaux à forte teneur en Si, souvent difficiles à obtenir et mettre en forme industriellement. Des alliages magnétiques doux de type Fe-Si avec une teneur élevée en Si (4,5%, 6,5%, 10% et 15% massique) ont été obtenus avec succès à l’état nanocristallin par broyage mécanique et recuit. La formation des alliages a été étudiée par diffraction X, spectroscopie Mössbauer et analyses thermomagnétiques. La stabilité thermique de la poudre a été analysée par DSC. Des mesures d’aimantation ont été réalisées pour caractériser les performances magnétiques. La durée de broyage nécessaire pour la formation de l’alliage a été déterminée pour chaque teneur en Si. Pour les faibles temps de broyage, le recuit conduit à la formation du composé Fe3Si. Après la formation de l’alliage par le broyage mécanique, l’effet du recuit est seulement de réduire les tensions internes du second ordre, induites dans la poudre par le broyage. L’addition de Si conduit à la diminution de la température de Curie de 770 °C pour le Fe pur, à 725 °C pour une teneur de 4,5% massique de Si et à 550 °C pour 15% massique de Si. Pour les temps faibles de broyage, l’écart entre l’aimantation de la poudre avant et après recuit est dû à la formation du composé Fe3Si pendant le recuit, lequel a une aimantation plus faible que la solution solide de Feα(Si). Pour les longs temps de broyage, le recuit à 400 °C pour 4 heures n’a pas d’effet sur la valeur de l’aimantation à saturation. En augmentant la teneur en Si, l’aimantation à saturation de l’alliage Fe-Si décroit.Les alliages Ni3Fe (aussi connus comme Permalloys) présentent de meilleures propriétés magnétiques, mais ils ont une résistivité inférieure à celles des Fe-Si. Une voie attractive semble la combinaison des propriétés des 2 classes de matériaux doux en formant un composite. Les alliages Fe-Si précédemment obtenus ont été utilisés pour l’élaboration des poudres composites de type Permalloy/Fe-Si par la mécanosynthèse. Le broyage mécanique conduit à la formation des particules composites avec un aspect stratifié. Quatre heures de broyage de l’alliage Fe-Si avec du Ni3Fe ne conduisent pas à la formation des nouvelles phases, mais la formation d’un alliage ternaire Ni-Fe-Si résulte d’un recuit ultérieur à 900 °C. L’aimantation à saturation du composite augmente avec la croissance de la teneur le d’alliage Fe-Si, mais le temps de broyage ne semble avoir aucun effet sur cela.Une étude préliminaire a été réalisée sur l’élaboration des compacts composites de type Ni3Fe/Fe-Si par frittage flash, dans le but de préserver l’état nanocristallin par de basses températures de frittage. L’influence de la température de frittage et de la durée de maintien sur la structure, et les propriétés physiques des compacts est discutée. Des températures allant jusqu'à 750 °C pour une durée de maintien minimale ou un palier de 2 minutes maximum à 700 °C ne conduisent pas à la diffusion des éléments des alliages. L'augmentation de la température ou de la durée de frittage conduit à des cristallites plus grandes, mais qui restent dans le domaine nano pour les températures étudiées. La densité des compactes augmente avec la température et le palier. En outre, la résistivité diminue en augmentant ces 2 paramètres. L'effet de la teneur en Fe-Si est de diminuer la densité et en même temps d'augmenter la résistivité des compacts. La perméabilité magnétique est réduite avec l'augmentation de la température et de la durée de frittage, ainsi que lors de la diminution du contenu de Ni3Fe. Une température élevée et un long temps de maintien à la température de frittage conduisent à l’augmentation des pertes magnétiques. Le champ coercitif est également influencé par les paramètres de frittage, via l'effet qu'ils ont sur la taille des cristallites. / Fe-Si alloys are known for combining excellent magnetic properties with good electric characteristics (high resistivity). In this context we sought to develop materials with a relatively high Si content, often difficult to obtain and shape industrially.In this thesis, soft magnetic Fe-Si alloys with high Si content (4.5, 6.5, 10 and 15 wt. %) were successfully obtained in nanocrystalline state by mechanical alloying and annealing. The formation of the alloy was studied by X-ray and neutron diffraction, Mossbauer spectroscopy and thermomagnetic analysis. DSC technique was used in order to study the powder’s thermal stability. Magnetisation measurements were also made in order to characterise their magnetic performances. The milling duration necessary for the formation of the alloy was determined for each Si content. For low milling times, annealing leads to the formation of the Fe3Si compound. Once the alloy is formed by mechanical milling, the effect of the annealing is only to reduce the second order stress induced in the powder by the milling process. Si addition leads to the decrease of the alloy’s Curie temperature from 770 °C for pure Fe to 725 °C for a 4.5 wt. % Si and down to 550 °C if the Si content increases to 15 wt. %. For low milling times, a gap between the magnetisation of the as-milled alloy and of the milled and subsequently annealed one is due to the formation of the Fe3Si compound during annealing which has a lower magnetisation than that of the αFe (Si) solid solution. For longer milling durations, annealing at 400 °C for 4 hours has no effect on the saturation magnetisation value. By increasing the Si content, the Fe-Si alloy’s saturation magnetisation decreases.Fe-Ni alloys whose composition is close to Ni3Fe (commonly known as Permalloys) have better magnetic properties, but a resistivity well inferior to that of Fe-Si alloys. Therefore, a combination of the properties of these 2 alloy classes of soft magnetic materials into a composite seems to be an attractive route. The previously obtained Fe-Si alloys were used for the preparation of Permalloy/Fe-Si composite powders by mechanical milling. Milling leads to the formation of composite powder particles with a stratified aspect. Milling of the Fe-Si and Ni3Fe alloys for 4 hours does not lead to the formation of new phases, but a subsequent annealing at 900 °C results in the formation of a Ni-Fe-Si alloy. Saturation magnetisation of the composite increases with increasing of the Fe-Si content, but milling duration seems to have no effect on it.A preliminary study was made on the elaboration of Ni3Fe/Fe-Si composite compacts obtained by spark plasma sintering, aiming to preserve the nanocrystalline state by lower sintering temperatures. The influence of the sintering temperature and temperature holding duration on the structure, density, resistivity and magnetic properties of the compacts is discussed. Temperatures of up to 750 °C for minimal holding duration or a maintain at the temperature of 700 °C for a duration of up to 2 minutes does not lead to a diffusion of the alloys’ elements. Increasing of the sintering temperature or duration leads to larger crystallite sizes, but they remain in the nano domain for the studied temperatures. The compacts’ density increases with temperature and sintering duration. Resistivity, on the other hand decreases when increasing the aforementioned parameters. The effect of the Fe-Si content is to decrease the density and at the same time increase the compacts’ resistivity. Magnetic permeability is reduced with increasing sintering temperature and duration, as well as when decreasing of the Ni3Fe content. High temperature and long maintaining duration leads to an increase of magnetic losses. Coercive field is also influenced by sintering parameters by the effect they have on the crystallite size.

The main objective of present diploma thesis is to prepare three different classes of steels, differing by their content of chromium: 9Cr, 14Cr, 17Cr steels and their oxide dispersion strengthened variants. Steels were prepared from atomic and pre-alloyed powders by the mechanical alloying and compacted by the spark plasma sintering method. Used strengthening elements were yttrium, which is most commonly used, and aluminium. Preparation of oxide dispersion was done in two ways: direct adding of yttria and alumina and inner oxidation of aluminium and yttrium. In the experimental part has been found, that it is possible to make oxide dispersion by both ways, but aluminium strengthened steel has to be prepared by inner oxidation to ensure fine oxide dispersion.

This thesis deals with topic of high entropy alloys. The teoretical part explains what are high entropy alloys, how are they different from conventional alloys, how is their chemical composition proposed and what potencial these alloys have. The experimental part describes procedures of preparation of three high entropy alloys witch consists of Co, Cr, Fe, Ni and Ti, where the concentration of all elements except Ti remains the same. These alloys were prepared via mechanical alloying and sintered by SPS process. Crucial part of this thesis is characterization of these three alloys with EDS and XRD supported by hardness measuring and tensile tests.

This diploma thesis deals with the preparation of new high-temperature resistant cermets based on TiB2. The hard ceramic phase is bonded by NiW metallic alloy, which was prepared by mechanical alloying using a planetary ball mill. The first part of the thesis is targeted to the optimization of mixing of both powders in the planetary ball mill. The procedure of preparation of powders mixture with homogenous particles distribution of the NiW alloy was designed and verified with simultaneous particle size refinement. The second part is focused on the microstructure characterisation and mechanical properties evaluation of sintered materials. In this case both powders, TiB2 and NiW, were mixed in a tubular mill and consequently compacted by a rapid hot pressing method at four different sintering temperatures. The influence of the sintering temperature on the microstructure development characterized by the density, porosity and grain size was monitored. The elastic modulus, fracture toughness, flexural strength and hardness were measured on prepared test specimens. The results of conducted experiments show a significant dependence of the microstructure and mechanical properties on applied sintering temperatures. The higher sintering temperatures are used the better mechanical properties are observed. However, the sintering temperature of 1375°C seems to be an optimal one. The sintering temperature of 1400°C leads to the significant losses of the metal phase due to sublimation of nickel resulting in increased porosity in the metal phase regions.

More efficient and cheaper solar cells are necessary if photovoltaics are to play a major rolein the field of sustainable power generation. Copper indium gallium selenide (CIGSe) is one of the best suited materials for thin film solar cell absorbers. One production method for thin film manufacturing is sputtering, a fast, high-yield, all-dry process that can be performed in an unbroken vacuum chain. The sputter target, which provides the raw material for this process, is an important link to obtain high quality films. Furthermore, the targets stands for the single largest cost in solar cells produced through the method. Hence, driving down the target production costs while maintaining or increasing quality is a vital route towards competitive photovoltaic power generation. In this project, compound CIGSe sputter target material was produced via mechanical alloying of elemental raw materials, followed by hot pressing. The resulting material obtained a relative density above 90% in all samples, with close compositional matching and grain sizes between 20-50 µm. Electrical characterization indicated predominantly p-type majority carriers, and the resistivity was within the range of industrially produced targets. Suitable process parameters are suggested as follows: for ball milling; 600rpm rotational speed, a ball-to-powder ratio of 5:1, and a milling time of 60-120 min. For pressing: 650-750˚C peak temperature, maintained for 1-2 h under 25-60 MPa pressure. 30 min dwell time at peak temperature before pressure application was found to reduce porosity. An initial composition of 23.2/20/6.5/50 at% of Cu, In, Ga, and Se, respectively, was found appropriate to obtain a final composition close to 22.8/20/7/50.2 at%. The project has proven that mechanical alloying combined with hot pressing provides a promising route towards efficient sputter target manufacturing, where the reduction of process operations compared to conventional manufacturing methods entails an optimistic economic outlook.

With growing world population and decreasing fossil fuel reserves we need to explore and utilize variety of renewable and clean energy sources to meet the imminent challenge of energy crisis. Solar energy is considered as the leading promising alternate energy source with the pertinent challenge of off sunshine period and uneven worldwide distribution of usable sun light. Although thermoelectricity is considered as a reasonable energy harvester from wasted heat, its mass scale usage is yet to be developed. By transforming window glasses into generators of thermoelectricity, this doctoral work explores engineering aspects of using the temperature gradient between the hot outdoor heated by the sun and the relatively cold indoor of a building for mass scale energy generation. In order to utilize the two counter temperature environments simultaneously, variety of techniques, including: a) insertion of basic metals like copper and nickel wire, b) sputtering of thermoelectric films on side walls of individual glass strips to form the thickness depth of the glass on subsequent curing of the strips, and c) embedding nano-manufactured thermoelectric pillars, have been implemented for innovative integration of thermoelectric materials into window glasses. The practical demonstration of thermoelectric windows has been validated using a finite element model to predict the behavior of thermoelectric window under variety of varying conditions. MEMS based characterization platform has been fabricated for thermoelectric characterization of thin films employing van der Pauw and four probe modules. Enhancement of thermoelectric properties of the nano- manufactured pillars due to nano-structuring, achieved through mechanical alloying of micro-sized thermoelectric powders, has been explored. Modulation of thermoelectric properties of the nano-structured thermoelectric pillars by addition of sulfur to nano-powder matrix has also been investigated in detail. Using the best possible p and n type thermoelectric materials, this novel energy generation technique promises 304 watts of thermoelectricity from a 9 m2 glass window utilizing temperature difference of 20 OC. In addition to be useful even during off sunshine hours of the day, these energy harvesting windows will be capable of power generation even in the absence of a cooling systems inside the building as long as a natural temperature gradient exists between the two counter environments. With an increasing trend of having the exterior of buildings and high rises entirely made up of glass, this work offers an innovative transformation of these building exteriors into mass scale energy harvesters capable of running average lighting loads inside the building hence providing a complimentary source of electricity to the main power grid.