Manganese (Mn) oxides, widely found in aquatic and terrestrial environments, play crucial roles in natural ecosystems and in environmental processes. Previously, it was believed that naturally abundant Mn oxides originated through biotically mediated processes. However, we have revealed the significance of photochemically induced abiotic oxidation of Mn2+(aq) to Mn(IV) oxides. This study further elucidates the photochemically induced co-oxidation of aqueous Mn2+ and cobalt (Co2+), which leads to the predominant formation of Mn(IV)–Co(III) oxide nanosheets. Both pair distribution function analysis and X-ray absorption spectra provide evidence that Co2+ is mainly oxidized to Co(III) within the plane of the Mn oxide structure, where it forms double-edge-sharing arrangements. Additionally, the initial concentration of Co2+ greatly influences the extent of Co incorporation within the final Mn–Co oxides and Mn oxidation states. Increased Co incorporation correlates with a higher concentration of oxygen vacancies within the Mn oxide structures, which reduces their band gap and significantly influences the reactivity of Mn oxides, governing their ability to participate in pollutant degradation and redox transformations. This study advances our understanding of the mechanism of formation of Co-incorporated Mn oxides in the natural environment and provides insights into their occurrence in the natural environment and their applications in environmental processes.
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Oxide Stability Analysis and Characterization in a Galvannealed Dual-Phase Steel Exhibiting Coating Defects
As more emphasis is placed on thinner gauges and stronger steel grades for more fuel efficient, and crash-worthy vehicles, corrosion becomes a more important consideration. This demand has led to the development of advanced high strength steel (AHSS) grades such as dual-phase (DP) and transformation-induced plasticity (TRIP) aided steels. To protect these steels from corrosion, a hot-dip galvanizing (HDG) or galvannealing (GA) process is employed. However, alloying with Mn and Si can cause complex surface oxides during annealing, which may result in defects in the zinc coating1-8. In order to increase AHSS galvanizability, selective oxidation of alloying elements in DP and TRIP-aided steel needs to be understood. Depending on annealing atmosphere, the mechanism (internal or external) of oxidation can change, as well as the thermodynamic stability of the oxide. Wagner’s theory of oxidation enables prediction of the mechanism of oxidation for binary oxide systems9. The defects can be present after pickling and fluxing, causing wettability issues during the HDG process. Coating defects may also form or be further exacerbated by the galvannealing operation. For this work, oxidation mechanism predictions were performed using Wagner’s theory of oxidation. In the present study a 0.07C-1.9Mn-0.2Si-0.3Cr galvannealed dual-phase steel which exhibited streaking defects in the coating was analyzed. Light optical metallography (LOM) and scanning electron microscopy (SEM) were performed to characterize defects within the galvannealed coating. Static spectra and 3-D profiling using time of flight secondary ion mass spectrometry (TOF-SIMS) was employed. It was found that Mn rich Si containing oxides are present on the steel-coating interface. It does not appear that these oxides affect wettability, however they may have an influence on intermetallic growth during galvannealing. This, combined with an influence from the micro-grooves of the sink roll in the Zn pot, may lead to the streaking defects observed.
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- Award ID(s):
- 1726898
- PAR ID:
- 10122052
- Date Published:
- Journal Name:
- 2019 AISTech Conference Proceedings
- Page Range / eLocation ID:
- 1819 to 1828
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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