Charging-induced formation of vacancy-type defects in LixCoO2 battery cathodes was studied by the defect-specific techniques of positron lifetime spectroscopy and Doppler broadening of positron–electron annihilation radiation. The regime of reversible charging is dominated by vacancy-type defects on the Li+-sublattice the size of which increases with increasing Li+-extraction. Indication is found that Li+-reordering which occurs at the limit of reversible Li+-extraction (x = 0.55) causes a transition from two-dimensional agglomerates into one-dimensional vacancy chains. Degradation upon further Li+-extraction is accompanied by the formation of vacancy complexes on the Co- and anion sublattice.
In order to improve the mechanical properties at elevated temperatures, several types of steels are mechanically alloyed with yttria. The processes that are active during milling differ dependent on the individual powder constituents. Nevertheless, some theories exist which try to describe the mechanism of producing a metastable phase during milling. However, even in the system iron–yttria, the mechanisms taking place during milling are still not well understood. By using the example of a simple iron–yttria model alloy, this paper attempts to elucidate the structure of mechanically milled powder particles and, consequently, to clarify the functionality of mechanical alloying in the last stage of milling. Positron annihilation experiments on milled materials revealed “open” volumes which are enriched in yttria. Electron backscatter diffraction and atom probe tomography as complimentary techniques allowed an identification of these “open” volumes as mainly vacancies, where enrichments of Y and O occur. From these results, it can be concluded that especially vacancies are responsible for producing a metastable phase, whereby yttria is dissolved in pure iron.
The influence of high-pressure torsion (HPT) on the microstructure and free-volume type defects of supersaturated Al-3 wt%Cu was studied. By means of HPT, grain refinement down to sizes of 100 nm could be achieved. Positron annihilation spectroscopy was applied for the characterization of deformation-induced defects and of vacancy-solute interaction. The chemical sensitive method of two-dimensional Doppler broadening spectroscopy reveals predominantly deformation-induced defects. In comparison to undeformed supersaturated Al-3 wt%Cu, the fraction of Cu-decorated free-volume type defects is strongly reduced and Al2Cu-precipitates with equilibrium structure occur rather than metastable semi-coherent Al-Cu precipitates. These precipitates stabilize the nanocrystalline structure and give rise to a rather different aging behaviour compared to the undeformed state.
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