Les poudres d'aluminium sont depuis longtemps utilisées comme additifs dans de nombreuses formulations pour la pyrotechnie ou les propergols. Introduites en quantité relativement faible dans les propergols des fusées, elles permettent d'accroître significativement les vitesses de combustion. Cependant, les mécanismes à l'origine de cette meilleure réactivité restent encore mal compris et vont bien au-delà d'une simple explication en terme d'augmentation de l'état de division. Au cours de cette thèse nous avons élaboré des poudres d'aluminium par broyage à haute énergie, technique mécanique peu couteuse qui pourrait être une alternative aux procédés de fabrication actuels. Nous montrons que cette méthode permet l'obtention de particules micrométriques ou nanométriques suivant les conditions de broyage. Les particules sont polycristallines et présentent une morphologie en plaquette. Les poudres nanométriques obtenues présentent une réactivité comparable voire même supérieure aux nanopoudres sphériques actuellement élaborées par électro-explosion de fil ou voie plasma. Nous montrons que cette bonne réactivité est lié à la morphologie des particules ainsi qu'à la microstructure de la couche d'alumine native qui passive l'aluminium. / Aluminium nanopowders have been using for a long time as additives in many formulations for propergol or in pyrotechnics. Introduced in small quantity in rocket propergol they allow to increase the combustion rate. However, the reactivity of aluminium particles is not really understood and not just linked to the size reduction effect. All along this study, we have elaborated aluminium powders using high energy mechanical milling, a mechanical technique with a low cost which could be an alternative process of powders fabrication. We prove that this method allows elaboration of micro and nano-particles as a function of the mechanical parameters. The particles are polycristallines with flake morphology. The obtained nanopowders have a similar reactivity, or better than spherical nanopowders obtained by wire electrical explosion or plasma. We proove that this good reactivity is linked to the particles morphology, as well as also to the microstructure of the native alumina core shell.

Made available in DSpace on 2017-07-21T20:42:32Z (GMT). No. of bitstreams: 1 Melina Correa Gabriel.pdf: 5915390 bytes, checksum: bae67fca28fd7999823fa6ec6ac98844 (MD5) Previous issue date: 2010-03-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The intention of this exploratory research is to study the modifications provided by high-energy mechanical milling in ultra-high molecular weight polyethylene (UHMWPE) and mixtures of this polymer with polyethylene glycol (PEG). These modifications can be of interest for future processing of UHMWPE. The mechanical milling was performed in an attritor mill, a type of mill that can be used in laboratory as well as in industry. The millings of UHMWPE were performed in different rotation speeds. For mixtures of UHMWPE and PEG, the amounts of PEG were also different. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The mechanical milling modified the UHMWPE particles morphology: with milling, the almost rounded shape became flat-like shape. This caused the reduction of apparent density of polymer after milling. The mechanical milling also provided structural changes. With the increasing of the rotation speed,there was the increasing of the monoclinic phase and the decreasing of the orthorhombic, up to 500 rpm. For 600 rpm, the amount of monoclinic phase decreased. In this rotation, the deformation rate probably increased the process temperature, allowing the monoclinic phase to return to its initial structural orthorhombic form. In mixtures of UHMWPE and PEG, after mechanical milling, the particles of PEG were probably reduced and better dispersed in the UHMWPE matrix. Changes in thermal characteristics of polymers also could be noted. The kinetics of UHMWPE crystal growth changed, as well as the behavior of PEG crystallization. Feasibly, dispersed particles of PEG acted as physical barriers against the crystalline phase growth of UHMWPE and the crystallization temperature of PEG decreased, when the UHMWPE and PEG mixtures were milled. / Este trabalho exploratório teve por objetivo estudar as modificações promovidas por moagem de alta energia no de polietileno de ultra-alta massa molar (PEUAMM) e sua mistura com polietileno glicol (PEG), que podem ser de interesse para auxiliar um posterior processamento do PEUAMM. As moagens foram realizadas em um moinho do tipo attritor, um tipo de moinho que pode ser usado tanto em laboratório quanto em escala industrial. Foram variadas as velocidades de rotação na moagem do PEUAMM, além das concentrações de PEG, quando feita a mistura. As amostras foram caracterizadas por microscopia eletrônica de varredura (MEV), microscopia de força atômica (MFA), calorimetria exploratória diferencial (DSC) e difração de raios X. A moagem de alta energia do material modificou a forma das partículas de PEUAMM, passando de arredondadas a flakes, com a evolução do processo de moagem, fazendo com que a densidade aparente do polímero diminuísse muito comparado ao polímero não moído. A moagem também proporcionou mudança estrutural, permitindo a formação de fase monoclínica em detrimento da ortorrômbica. A medida que se aumentou a rotação do moinho até 500 rpm, houve um crescimento da fase monoclínica. Apenas para 600 rpm, a quantidade dessa fase sofreu decréscimo, devido possivelmente ao aumento da frequência de choques e da temperatura de processamento, fazendo com que a estrutura monoclínica retornasse à estrutura ortorrômbica original. Na mistura de PEUAMM com PEG, a moagem provavelmente permitiu redução das partículas e a melhor dispersão de PEG na matriz de PEUAMM. Também se observaram mudanças nas características térmicas dos polímeros na mistura após moagem. Ocorreu mudança na cinética de crescimento dos cristais de PEUAMM e mudança no comportamento de cristalização do PEG, comportamento este que não ocorreu para o PEUAMM moído ou para a mistura de PEUAMM com PEG antes da moagem. Possivelmente, as partículas dispersas de PEG atuaram como barreiras ao crescimento da fase cristalina do PEUAMM e houve diminuição da temperatura de cristalização do PEG, na mistura com PEUAMM após moagem.