Abstract

Structural defects play a major role in nanotechnology as they influence most properties, thus largely motivating the special interest in studying materials at the nano scale. The present Thesis work contributes to this broad and diversified research field with emphasis on the characterization of nanocrystalline ceramic materials and their lattice defects. In particular, main efforts were addressed to develop new and more comprehensive approaches to the study of nanocrystalline powders, combining different techniques for a better and deeper understanding of materials. The specific applications selected in this work are basically two: nanocrystalline fluorite as a promising ionic conductor and nanocrystalline magnesium hydride for hydrogen storage applications. Chapters II and III were dedicated to investigate nanocrystalline fluorite produced by two different methods: a bottom-up approach based on co-precipitation of Ca and F precursors yielding loosely bound nanocrystals, and a popular top-down approach, high energy ball milling, giving nanocrystals of comparable sizes but strongly agglomerated and densely populated with dislocations. As a major achievement reported in this part of the Thesis work, a new approach was proposed and tested for the simultaneous modelling of X-ray Diffraction (XRD) peak profiles and solid state NMR spin-lattice relaxation data. With the valuable support of Transmission Electron Microscopy (TEM), this work offers a new understanding of the complex defect structure of nanocrystalline fluorite, and is also a demonstration of the power of combining different techniques in a consistent way. One of the most debated aspects of nanotechnology concerns the stability of the nanostructure, and the mechanisms of defect annealing and grain growth with temperature. This topic was the object of chapter V, dedicated to study the influence of lattice defects on the grain growth kinetics of nanocrystalline fluorite. This chapter was preceded by chapter IV, on the furnace recently installed at the MCX beamline for in-situ high temperature fast data collection; besides providing useful details for the in-situ study on nanocrystalline fluorite shown in the following chapter, the activity reported in chapter IV is a tangible sign of the special involvement during the Thesis work in supporting standard operation as well as development of the ELETTRA beamline MCX. The growth kinetics was studied on two samples, among those discussed in Chapter III, with comparable crystalline domain size but drastically different lattice defect content, so to highlight the role lattice defects – dislocations in this case – in the growth process. 14 Last two chapters (chapter VI and VII) were dedicated to nanocrystalline magnesium hydride, and how the performance, in particular the hydrogen desorption kinetics, can be improved by adding a nanocrystalline tin oxide. Besides general aspects on phase composition of the system and hydrogen storage capability, the work also addressed the problem of obtaining activation energy values in the thermal decomposition of magnesium hydride powders, presenting an interesting review of results given by the most known and well-assessed TG-MS coupled measurements, with details on the use of different equations of the literature on thermal analysis. Although research work can rarely be considered as finished, a sound conclusion of this Thesis work is toward the use of different characterization techniques, also within the same data analysis procedure, to support a better, and more reliable investigation of nanomaterial properties.