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Abstract Directional freeze‐cast Fe‐W lamellar foams with 10–33 at.% W show distinct microstructural evolutions during steam/hydrogen redox cycling between oxidized and reduced states at 800 ⁰C, depending on W concentration. The Fe‐18 W and Fe‐25 W foams exhibit a sufficient volume fraction of W‐rich phases – λ‐Fe2W to inhibit sintering for α‐Fe in the reduced state and FeWO4to inhibit sintering for Fe3O4in the oxidized state – thus forming ligaments comprising two phases (Fe/λ‐Fe2W and Fe3O4/FeWO4, respectively). In contrast, a Fe‐10 W foam with a lower volume fraction of W‐containing phases (λ‐Fe2W and FeWO4) shows lamellae densification as well as core‐shell structure formation, due to Fe outward diffusion during oxidation. While higher W concentration enhances the stability of lamellar structure in Fe‐W foams, degradation still occurs, via buckling of lamellae and swelling of foams after extensive cycling. In situ XRD characterization shows that W addition has a minor effect on the oxidation process but slows reduction due to the sluggish kinetics of FeWO4reduction. This influence is mitigated by the formation of nanocrystalline W‐rich phases due to the chemical vapor transport (CVT) mechanism during the reduction of FeWO4to boost the reaction kinetics during redox cycling.
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Asymmetric nanoparticle oxidation observed in-situ by the evolution of diffraction contrast
Abstract The use of transmission electron microscopy (TEM) to observe real-time structural and compositional changes has proven to be a valuable tool for understanding the dynamic behavior of nanomaterials. However, identifying the nanoparticles of interest typically require an obvious change in position, size, or structure, as compositional changes may not be noticeable during the experiment. Oxidation or reduction can often result in subtle volume changes only, so elucidating mechanisms in real-time requires atomic-scale resolution orin-situelectron energy loss spectroscopy, which may not be widely accessible. Here, by monitoring the evolution of diffraction contrast, we can observe both structural and compositional changes in iron oxide nanoparticles, specifically the oxidation from a wüstite-magnetite (FeO@Fe3O4) core–shell nanoparticle to single crystalline magnetite, Fe3O4nanoparticle. Thein-situTEM images reveal a distinctive light and dark contrast known as the ‘Ashby-Brown contrast’, which is a result of coherent strain across the core–shell interface. As the nanoparticles fully oxidize to Fe3O4, the diffraction contrast evolves and then disappears completely, which is then confirmed by modeling and simulation of TEM images. This represents a new, simplified approach to tracking the oxidation or reduction mechanisms of nanoparticles usingin-situTEM experiments.
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- Award ID(s):
- 2240407
- PAR ID:
- 10469878
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- Journal of Physics: Materials
- Volume:
- 6
- Issue:
- 4
- ISSN:
- 2515-7639
- Format(s):
- Medium: X Size: Article No. 045013
- Size(s):
- Article No. 045013
- Sponsoring Org:
- National Science Foundation
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