Hydrogen storage in mgh2-additives (additives: fe, nb, fe2o3, nb2o5, fef3, nbf5) nanocomposites produced by high energy ball milling and severe plastic deformation

Nanocompositos a base de magnesio sao considerados materiais muito promissores para a armazenagem de hidrogenio em estado solido. No presente trabalho, nanocompositos a base de magnesio contendo aditivos a base de Ferro (Fe, Fe2O3, FeF3) e Niobio (Nb, Nb2O5, NbF5) foram processados por diferentes rotas de processamento envolvendo tecnicas de moagem de alta energia (MAE) e deformacao plastica severa (SPD). As tecnicas de MAE sao representadas aqui pela moagem reativa (MR) sob atmosfera de hidrogenio e pela moagem criogenica (MC) enquanto que a tecnica de SPD e representada pela laminacao a frio (CR). Uma nova rota alternativa de processamento composta por uma etapa previa curta de moagem antes do processo de laminacao foi avaliada. O estudo da influencia de aditivos conforme a rota de processamento empregada e a intensa caracterizacao das propriedades de armazenagem de hidrogenio permitiu um melhor entendimento sobre os mecanismos responsaveis pelas melhorias cineticas relacionadas com as particularidades microestruturais. Os materiais preparados pelos diferentes tecnicas de processamento foram caracterizados atraves de tecnicas de analise micro e nanoestrutural, incluindo, entre outras, difracao de raios-X (DRX) seguida pelo metodo de Rietveld, microscopia eletronica de varredura e transmissao. O comportamento durante a dessorcao foi estudado por calorimetria diferencial de varredura (DSC) e a cinetica das reacoes foram investigadas atraves de ciclos de absorcao/dessorcao de H2. A correlacao entre os resultados obtidos com as diferentes rotas de processamento demonstraram que o efeito benefico dos aditivos em promover a cinetica das reacoes com o H2 se estende de maneira muito positiva independentemente da rota de processamento usada, porem, os mecanismos de atuacao dependem estritamente dos metodos de preparacao e da combinacao de um ou mais fatores relacionados a microestrutura. Alem disso, as tecnicas de SPD demonstraram um grande potencial frente as tecnicas de MAE no processamento de nanocompositos a base de magnesio, resultando em materiais com otimas propriedades de armazenagem de hidrogenio.Mg-based nanocomposites are considered promising materials for hydrogen storage in the solid state. In this work, Mg-based nanocomposites containing iron-based (Fe, Fe2O3, FeF3) and niobium-based (Nb, Nb2O5, NbF5) additives were processed by different processing routes involving high energy ball milling and severe plastic deformation techniques. The high energy ball milling techniques are represented here by the reactive milling under hydrogen atmosphere and by the cryogenic milling while the severe plastic deformation technique is represented here by extensive cold rolling. An alternative processing route including a previous short ball milling step before the cold rolling processing was evaluated. The study of the effect of additives according to the chosen processing routes and an extensive characterization of the hydrogen storage properties allowed a better understanding on the mechanisms which are responsible by the kinetics improvements related to the microstructural particularities. The materials prepared by the different processing techniques were characterized by micro and nanostructural analysis techniques such as, among others, x-ray diffraction followed by the Rietveld method, scanning and transmission electron microscopy. The desorption behavior was studied by differential scanning calorimetry and the kinetic behavior was investigated by absorption and desorption cycles. The correlation of the results obtained with the different processing routes showed that the beneficial effect of the additives in promoting the H-sorption kinetics is positively extended independently of the processing route; however, the acting mechanisms depend on strictly on the preparation methods and the combination of one or more factor related to the microstructure. Furthermore, the severe plastic deformation techniques showed a very good potential in comparison with the high energy ball milling techniques in processing Mg-based nanocomposites, resulting in materials with good hydrogen storage properties