Water adsorption and surface protonic conduction have been investigated at 25 – 400 oC in wet (H2O and D2O) atmospheres on nanocrystalline TiO2 hydrothermally grown to a predominance of different...
We used a range of advanced microscopy techniques to study the microstructure, nanoscale chemistry, and porosity in zirconium alloys at different stages of oxidation. Samples from both autoclave and in-reactor conditions were available, including ZIRLO™, Zr-1.0Nb, and Zr-2.5Nb samples with different heat treatments. Scanning transmission electron microscopy (STEM), transmission Kikuchi diffraction (TKD), and automated crystal orientation mapping with TEM were used to study the grain structure and phase distribution. Significant differences in grain morphology were observed between samples oxidized in the autoclave and in-reactor, with shorter, less well-aligned monoclinic grains and more tetragonal grains in the neutron-irradiated samples. A combination of energy-dispersive X-ray mapping in STEM and atom probe tomography analysis of second-phase particles (SPPs) can reveal the main and minor element distributions respectively. Neutron irradiation seems to have little effect on promoting fast oxidation or dissolution of β-niobium precipitates but encourages the dissolution of iron from Laves-phase precipitates. An electron energy-loss spectroscopy (EELS) analysis of the oxidation state of niobium in β-niobium SPPs in the oxide revealed the fully oxidized Nb5+ state in SPPs deep into the oxide but Nb2+ in crystalline SPPs near the metal-oxide interface. EELS analysis and automated crystal orientation mapping with TEM revealed Widmanstatten-type suboxide layers in some samples with the hexagonal ZrO structure predicted by ab initio modeling. The combined thickness of the ZrO suboxide and oxygen-saturated layers at the metal-oxide interface correlated well to the instantaneous oxidation rate, suggesting that this oxygen-rich zone is part of the protective oxide that is rate limiting in the transport processes involved in oxidation. Porosity in the oxide had a major influence on the overall rate of oxidation, and there was more porosity in the rapidly oxidizing annealed Zr-1.0Nb alloy than in either the recrystallized alloy or the similar alloy exposed to neutron irradiation.
The influence of sulfur contamination on the corrosion-fatigue behavior of a polycrystalline superalloy used in aero-engines is considered. Samples tested under a variety of environmental conditions (including exposures to air, SO x gas, and salt) are characterized through a suite of high-resolution characterization methods, including transmission electron microscopy (TEM), secondary ion mass spectroscopy (nanoSIMS), and atom probe tomography (APT). The primary effect of sulfur contamination is to accelerate the crack growth rate by altering the failure mechanism. The SIMS and TEM analyses indicate Cr-Ti sulfide particle formation at grain boundaries ahead of and around oxidized cracks. The APT analysis suggests that these particles then oxidize as the crack propagates and are enveloped in chromia. The chromia is surrounded by a continuous layer of alumina within the cracks. All of the sulfur detected was confined within the particles, with no elemental segregation found at grain boundaries.
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