The oxidation state switching of cerium in cerium oxide nanoparticles is studied in detail. The influence of synthesis medium, aging time and local environment on the oxidation state switching, between +3 and + 4, is analyzed by tracking the absorption edge using UV-Visible spectroscopy. It is observed that by tuning the local environment, the chemistry of the nanoparticles could be altered. These time dependent, environmentally induced changes likely contribute to inconsistencies in the literature regarding quantum-confinement effects for ceria nanoparticles. The results in this article indicate that there is a need to carry out comprehensive analysis of nanoparticles while considering the influence of synthesis and processing conditions, aging time and local environment.
The large fraction of material residing at grain boundaries in nanocrystalline metals and alloys is responsible for their ultrahigh strength, but also undesirable microstructural instability under thermal and mechanical loads. However, the underlying mechanism of stress-driven microstructural evolution is still poorly understood and precludes rational alloy design. Here we combine quantitative in situ electron microscopy with three-dimensional atom-probe tomography to directly link the mechanics and kinetics of grain boundary migration in nanocrystalline Al films with the excess of O atoms at the boundaries. Site-specific nanoindentation leads to grain growth that is retarded by impurities, and enables quantification of the critical stress for the onset of grain boundary migration. Our results show that a critical excess of impurities is required to stabilize interfaces in nanocrystalline materials against mechanical driving forces, providing new insights to guide control of deformation mechanisms and tailoring of mechanical properties apart from grain size alone.
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