Resolving diverse oxygen transport pathways across Sr-doped lanthanum ferrite and metal-perovskite heterostructures

Perovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g. Ni- and Cr-based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real-world environments. Here we use isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal-perovskite heterostructures, i.e. (Ni-Cr coated) Sr-doped lanthanum ferrite (LSFO). Annealing in 18O2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni-Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory (DFT) calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. Our results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.Comment: 39 pages, 10 figure

In Situ Tem Mechanical Testing of Irradiated Oxide Dispersion Strengthened Alloys

The objective of this dissertation is to demonstrate the use of in situ TEM mechanical testing to find mechanical properties of as received, self-ion, and proton irradiated Fe-9%Cr ODS. The desire to work at small scale in the characterization of irradiated materials to reduce costs and improve throughput, require the development of novel methods to assess mechanical properties in volumelimited irradiation damage layers. Yet at these micrometer or nanometer scales, the mechanical properties can begin to be impacted by size effects. In this work micropillar compression, cantilever bending, lamellae indentation, and clamped beam fracture testing is conducted on ionirradiated Fe-9%Cr ODS to find yield stress, elastic modulus, flow stress, and fracture toughness. Micropillars in compression allow us to define a minimum sample dimension, which approaches the obstacle spacing of the material, at which size effects are observed. This relationship between sample dimension and obstacle spacing defined through micropillar compression is extended to a new testing geometry, cantilever bending, and material property, flow stress. Lessons learned during the cantilever bending informed the clamped beam design for conducting fracture testing on a ductile engineering alloy at micrometer scales. Finally, lamellae indentation was conducted to link qualitative observations of the microstructure under load with literature strength of obstacle values. By combining an understanding of the microstructure of irradiated Fe-9%Cr ODS and the in situ TEM technique, one can find the bulk-like mechanical properties of ion irradiated Fe-9%Cr ODS