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The performance of solid oxide cells is known to be dependent upon the density of three phase boundaries (TPB), but the potential for improving their effective electrocatalytic activity by morphological adjustments is imprecisely known. A spilling algorithm was developed to characterize the surfaces available for diffusion at TPBs. It scans each slice in a 3-D imaging dataset to measure the interfaces between the solid and the pore phases at each TPB. Because of the stereological approach, these surfaces are defined as "available lengths" (L-A). The measurement was tested on artificial packed spheres structures with controlled properties and a percolation theory-based model before application to a real Ni-YSZ. The L-A distributions cover 2 orders of magnitude. The subset shorter than the extent of diffusion profiles reported in the literature is in the range of 3% and 20% for Ni and YSZ, respectively, suggesting possible limitations of their effective electrocatalytic properties. The average L-A is larger on YSZ than on Ni, which is a trend opposite to the phase diameter. The available length analysis revealed microstructural characteristics that stem from the manufacturing route and cannot be identified by the inspection of standard metric and topological properties. A strong correlation between the available length and the extension of TPB lines is observed for Ni but not for YSZ, despite the predominance of convex shapes, which likely originates from the Ni reduction. This suggests possibilities for controlling the available length by the manufacturing route, depending specifically on the electrocatalytic properties of the phases in composite materials. (C) 2019 Acta Materialia Inc. Published by Elsevier Ltd.

This paper presents a novel 3D method to correct for absorption in energy dispersive X-ray (EDX) microanalysis of heterogeneous samples of unknown structure and composition. By using STEM-based tomography coupled with EDX, an initial 3D reconstruction is used to extract the location of generated X-rays as well as the X-ray path through the sample to the surface. The absorption correction needed to retrieve the generated X-ray intensity is then calculated voxel-by-voxel estimating the different compositions encountered by the X-ray. The method is applied to a core/shell nanowire containing carbon and oxygen, two elements generating highly absorbed low energy X-rays. Absorption is shown to cause major reconstruction artefacts, in the form of an incomplete recovery of the oxide and an erroneous presence of carbon in the shell. By applying the correction method, these artefacts are greatly reduced. The accuracy of the method is assessed using reference X-ray lines with low absorption.

The favorable growth kinetics of twinned dendrites can be explained by their complex morphology, multiple side branching mechanisms, growth undercooling and tip morphology. Three models were proposed for the twinned dendrite tip shape: (i) a grooved tip satisfying the Smith condition at the triple line; (ii) a doublon, i.e. a double-tip dendrite that grows with a narrow and deep liquid channel in its center; and (iii) a pointed (or edgy) tip, with consideration of the solid-liquid interfacial energy anisotropy. In the first part of this work, phase field simulations of half a twinned dendrite with an appropriate boundary condition to reproduce the Smith condition supported the doublon conjecture, with a narrow liquid channel ending its solidification with the formation of small liquid droplets. In this part, experimental observations of twinned dendrite tips reveal the presence of a small, but well-defined, groove, thus definitely eliminating the edged tip hypothesis. Focused ion beam nanotomography and energy-dispersive spectroscopy chemical analysis in a transmission electron microscope reveal the existence of a positive solute gradient in a region localized within 2 μm around the twin plane. In Al-Zn specimens, small particles aligned within the twin plane further support the doublon conjecture and the predicted formation of small liquid droplets below the doublon root. © 2011 Acta Materialia Inc.