The environmentally friendly n-type Mg2(Si, Sn) thermoelectric solid solutions have a strong potential of commercial utilization in thermoelectric (TE) energy conversion due to their availability, low density (~3.02 g/cm3), and high stability at middle temperature range (400-600 ▫C) that are typically observed from waste heat dissipating systems. The bulk materials were prepared from element powders via slow cooking under vacuum condition and current-assisted hot-press sintering. Temperature vs time curves have been researched in this thesis for fully reacted magnesium-silicide & magnesium-stannide green ingots with doping materials i.e. antimony, bismuth by different doping ratios. These ingots were ground by a high energy ball miller, uniaxial cold pressed into half inch pallets and then sintered by Direct Current-assisted hot pressing. Different synthesis conditions such as ball milling, sintering time, pressure, have been compared by SEM images and XRD tests analysis to figure out optimized process parameters. Several samples’ thermal conductivities (κ) were plotted as a function of temperature to study different synthesis strategies and doping materials’ effects on phonon scattering inside bulk thermoelectric materials.

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.

In this thesis work, it was aimed to optimize the conditions to produce silicon carbide (SiC), from rice husks from Turkish Thrace Region, via pyrolysis. Rice husks, coked at 500oC, were high energy ball-milled prior to pyrolysis, in order to investigate the effects of ball-milling on pyrolysis temperature, pyrolysis time and morphology of the SiC produced. Samples of rice husks subjected to different ball milling conditions, were pyrolyzed at temperatures varying from 1500oC to 1600oC and for times varying from &frac12 / hour to 2 hours. Results of experiments showed that, ball-milling reduced the pyrolysis temperature and pyrolysis time to some extent. It was also experimentally shown that ball-milling favored the formation of SiC particles rather than formation of SiC whisker.

Compaction of polymer powders and polymer-based nanocomposites by uniaxial high-velocity cold compaction (HVC), by high-energy ball milling (HEBM) and using a novel technique, relaxation assists, was investigated with a focus on the process parameters, the compactibility characteristics, surface morphology and friction. The basic phenomena associated with HVC are explained and the general energy principle is introduced to explain the pull-out phenomenon, springback gradient, delay time, relative time of the pressure wave, and stick-slip phenomenon during the compaction process. Experimental results for different compaction profiles, different particle size distributions and different milling system for polymer-based nanocomposite are presented, showing the effect of varying the process parameters on the compacted material; the compactibility in the compacted bed, the uniformity of the compacted surface, the pull-out phenomenon, the springback gradient, the stick-slip phenomenon and the homogeneity of the dispersions of nanoparticles in the polymer powders in the solid state. It was found that the high-velocity compaction process is an interruption process and that the opposite velocity and pressure loss during the compaction process have a major influence on the quality of the compacted material. The relaxation assist device is a novel technique that has been successfully developed to improve the compaction process. The relaxation assists are parts of the piston and they are regarded as projectile supports. They are constructed of the same material as the piston, and the diameters are the same but the lengths are different. The relaxation assist device leads to an improvement in the compaction of powders, polymer powders and polymer-based nanocomposites by giving a more homogeneous opposite velocity and a better locking of the powder bed in the compacted form during the compaction process with less change in dimensions in the case of both homogeneous and heterogeneous materials. If the movement of the particles is restricted the powder bed attains a higher density and the total elastic springback is minimized. In addition, there is a more homogeneous dispersion of nanoparticles in the case of a heterogeneous material. A much better transfer of the pressure through the powder bed and a smaller loss of pressure lead to a more homogenous stick-slip of the particles and a higher sliding coefficient due to the overall friction during the compaction process. / QC 20100630

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.

No description available.

The in-situ synthesis of piezoelectric-reinforced metal matrix composites has been attempted with a variety of target matrix and reinforcement materials using reaction synthesis and high energy ball milling. Zinc oxide (ZnO) and barium titanate (BaTiO₃) have been successfully synthesized within copper and iron matrices in a range of volume percentages using reaction synthesis. The microstructures of these composites have been analyzed and found to partially consist of an interpenetrating microstructure. After considering experimental findings and thermodynamic issues involved with synthesis, ideal reaction system parameters have been identified that promote the creation of a composite with ideal microstructure and formulated composition. Reactive high energy ball milling has been used to create copper matrix composites reinforced with zinc oxide and copper matrix composites reinforced with lead titanate (PbTiO₃). The microstructures and compositions of each volume percentage formulation of the composite powders have been analyzed. In this work, several promising piezoelectric-reinforced metal matrix composite systems have been identified as having potential to be synthesized in an in-situ manner. / Master of Science

Made available in DSpace on 2017-07-21T20:42:32Z (GMT). No. of bitstreams: 1 dissertacao - arquivos para publicar.pdf: 1279347 bytes, checksum: a251737807cada580c8a5af0b1c88bff (MD5) Previous issue date: 2010-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work the ultra high molecular weight polyethylene grafting with maleic anhydride by ball milling process was studied. UHMWPE with molecular weight of 8x106 g.mol-1, maleic anhydride and benzoyl peroxide were used. The ball milling process was performed in Attritor and Spex mills. The milling time, peroxide concentration and, in case of Attritor mill, the rotation, were the variables studied. We used two distinct levels for each variable and all possible combinations were studied with the use of statistical analysis for better interpretation of the results. The residual maleic anhydride was extracted from the samples by soxhlet extractor with acetone as a solvent. FTIR, SEM, XRD and bulk density measurements were performed for characterization. FTIR results revealed that the UHMWPE graft with maleic anhydride occurred for the processing in both mills. In case of the Attritor mill, the milling time and the rotation were the most influent variables in UHMWPE grafting. The peroxide concentration also affected the process, but with less intensity. For the Spex mill processing, the milling time was the most influent variable in grafting process, with the peroxide concentration again affecting less the process. The ball milling modified the polymer particles morphology, transforming from sphere to flake like. This transformation occurred in different levels, being correlated with milling time and rotation in case of Attritor mill. According to the change in the shape of the polymer particles, the bulk density was also affected by the same variables. The polymer crystalline structure was studied by XRD, where the influence on the variables was determined for the formation of monoclinic and orthorhombic phases. It was found that for the Attritor mill, the milling process induces the formation of a monoclinic phase, but it proved independent of the variables involved in the ball milling process. To the Spex mill processing, no change was detected in the concentration of the monoclinic phase, probably due to the warming occurred in the process that promotes the monoclinic-orthorhombic inversion around 70 º C. The ball milling also affected the thermal properties of the polymer, such as temperature and enthalpy of melting and crystallization. In this case, any variable proved influential in differentiating these thermal properties of milled samples in different conditions. The only significant difference was observed between the thermal properties of the milled samples for the no milled sample. / No presente trabalho foi estudada a funcionalização do polietileno de ultra alta massa molar com anidrido maleico através do processo de moagem de alta energia. Utilizou-se o PEUAMM de massa molar de 8 milhões de gramas por mol, anidrido maleico e peróxido de benzoíla. As moagens foram realizadas nos moinhos Attritor e Spex e as variáveis envolvidas no processo foram o tempo de moagem, a concentração de peróxido e, no caso do moinho Attritor, a rotação. Foram utilizados dois níveis distintos para cada variável e todas as combinações possíveis foram estudadas, com a utilização de análise estatística para a melhor interpretação dos resultados. O anidrido maleico não reagido foi extraído das amostras moídas por meio de extrator soxhlet com o emprego de acetona. As caracterizações foram efetuadas através de FTIR, DSC, MEV, DRX e medidas de densidade aparente. Os resultados de FTIR das amostras revelaram que a funcionalização do PEUAMM com anidrido maleico ocorreu para o processamento em ambos os moinhos. No caso do moinho Attritor, o tempo de moagem e a rotação foram as variáveis mais influentes na funcionalização do PEUAMM. A concentração de peróxido também se mostrou influente no processo, mas de forma menos intensa. Para o processamento no moinho Spex, o tempo de moagem foi a variável mais influente no processo de funcionalização, com a concentração de peróxido novamente influenciando de maneira menos intensa. A moagem modificou a morfologia das partículas do polímero, transformando-as de aproximadamente esféricas para “flakes”. Esta transformação ocorreu em diferentes níveis, relacionados com o tempo de moagem e com a rotação do moinho no caso do Attritor. De acordo com a modificação no formato das partículas do polímero, a densidade aparente também foi afetada pelas mesmas variáveis. A estrutura cristalina do polímero foi estudada através dos dados de DRX, onde foi verificada a influência das variáveis na formação das fases monoclínica e ortorrômbica do polímero. Obteve-se que para o moinho Attritor o processo de moagem induziu a formação de fase monoclínica, mas sua quantidade se mostrou independente das variáveis envolvidas no processo de moagem. Para o processamento via Spex nenhuma mudança foi detectada na concentração da fase monoclínica, provavelmente devido ao aquecimento ocorrido no processo e que promove a reversão monoclínica-ortorrômbica por volta de 70ºC. A moagem também afetou propriedades térmicas do polímero, como temperaturas e entalpias de fusão e cristalização. Neste caso, nenhuma variável se mostrou influente para diferenciar tais propriedades térmicas das amostras moídas nas diferentes condições. A diferença significativa observada foi apenas entre propriedades térmicas de amostras moídas em relação à amostra não moída.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Neste trabalho realizou-se estudos em escala laboratorial de soluÃÃes sÃlidas, procedentes dos precursores Fe2O3, BaCO3 e SrCO3, atravÃs do processo de moagem mecÃnica de alta energia, foram produzidos com sucesso pÃs nanocristalinos de BaxSr1-xFe12O19 (onde 0 x 1)os quais atravÃs de estudos de suas propriedades estruturais, morfolÃgicas e elÃtricas foram caracterizados. As propriedades das hexaferritas do tipo M de bÃrio ou de estrÃncio sÃo de grande interesse nas aplicaÃÃes de magnetos permanentes, meios de registros magnÃticos, dispositivos de microondas, absorvedores e sensores. Essas soluÃÃes sÃlidas substitucionais, depois de moÃdas receberam procedimento cerÃmico tradicional (procedimento do estado sÃlido). A estrutura cristalina das amostras foram identificadas por difraÃÃo de raios-X (hexagonal) pertencem ao grupo espacial P63/mmc. Os dados de difraÃÃo de raios-X foram refinados pelo mÃtodo Reitveld. Fez-se uso da espectroscopia MÃssbauer para realizar a sondagem do ferro presente na estrutura cristalina, constatando-se o estado de oxidaÃÃo do ferro (Fe3+) presente nos materiais analisados e a geometria do sÃtio cristalino no qual està presente. A morfologia e o tamanho mÃdio dos espÃcimes, na forma de pastilhas, foram analisados por Microscopia EletrÃnica de Varredura [216 â 339 nm], assistida por Energia Dispersiva de Raios-X, para analise quÃmica elementar. Foi realizado o estudo da constante dielÃtrica (Kâ), do fator de perda dielÃtrica (tg ) e a propriedade de condutividade elÃtrica () As propriedades dielÃtricas e elÃtrica foram analisadas em funÃÃo da freqÃÃncia, a temperatura ambiente, numa faixa compreendida entre 100 Hz e 40 MHz. Nos resultados das propriedades dielÃtricas, constatou-se que a amostra BFO100 apresenta a maior constante dielÃtrica (Kâ = 394,79) e a maior condutividade elÃtrica ( = 1,98 . 10-5 -1.m-1), porÃm, a menor perda dielÃtrica verificou-se nas amostras BFO75 e BFO90 (em ambas 0,81). Em virtude da constante dielÃtrica observada o espÃcime BFO100 apresenta o melhor perfil para aplicaÃÃes de RF (radio freqÃÃncia). / In this work he took place studies in laboratorial scale of solid solutions, coming from the precursors Fe 2 O 3 , BaCO 3 and SrCO 3 , through the process of mechanical high-energy ball milling, were produced with success powders nanocrystalline o f Ba x Sr 1-x Fe 12 O 19 (where 0 ≤ x ≤ 1)os which were characterized through studies of their properties structural, morphologic and electric. The properties of the hexaferritas of the type barium M or of strontium they are of great interest in the applications of permanent magnetos, means of magnetic registrations, devices of microwaves, absorbers and sensor. Those solid substitucionais solutions, after prepared milled received traditional ceramic procedure (procedure of the solid state). The crystalline structure of the specimens was identified by diffraction of ray-X (hexagonal) they belong to the space group P63/mmc. The diffraction data of ray-X were refined for the method Reitveld. Use of the spectroscopy was made MÃssbauer to accomplish the survey of the present iron in the crystalline structure, being verified the state of oxidation of the iron (Fe3+) present in the analyzed materials and the geometry of the crystalline ranch in which it present. The morphology and the medium size of the specimens, in the form of tablets, they were observed by Scanning Electron Microscopy (SEM) [216-339 nm], attended by Energy Dispersive Ray-X (EDX), for it analyzes elementary chemistry. The study of the dielectric constant was accomplished (K'), of the factor of loss dielectric (tg δ) and the property of electric conductivity ( σ). The properties dielectrics and electric they were analyzed in function of the frequency, to room temperature, in a strip understood between 100 Hz and 40 MHz. In the re sults of the properties dielectrics, it was verified that the sample BFO100 shows the largest result of the dielectric constant (K ' = 394,79) and the largest electric conductivity (σ = 1,98. 10 -5 Ω -1 .m -1 ), however, to smallest loss dielectric it was verified in the samples BFO75 and BFO90 (in both 0,81). In virtue of the constant dielectric observed, the specimen BFO100 shows the best profile for applications of RF (I radiate frequency).

No description available.