Proton Radiation Effect on Iron Thermal Oxides: Point Defects, Microstructure & Corrosion Electrochemistry

Iron(Fe)-based alloys, such as austenitic stainless steels, form protective surface oxide layers when exposed to oxygen, aqueous electrolyte, and water vapor, which effectively inhibit corrosion [1]. One attribute that underpins the electrochemical reactivity of surface oxide layers is the presence and properties of charged point defects (e.g. vacancies and interstitials charge compensated by electrons or holes), which govern the rate and mechanism of ionic transport when exposed to an oxidizing environment such as an aqueous electrolyte [2,3,4]. However, the effect of radiation on the relationship between point defects, oxide microstructure, and oxidation behavior is poorly understood. Structural materials used in nuclear applications are particularly susceptible to radiation damage, which can degrade the underlying surface oxides. To investigate this phenomenon, thermally oxidized pure Fe was selected as a model material system to study radiation-induced defects in iron oxide scales [3]. Iron oxides were fabricated by thermal oxidation of pure Fe metal in air at 400°C, 600 o C, and 800°C for 1 hour. Each oxides layer exhibits an outer hematite (α-Fe 2 O 3 ) and inner magnetite (Fe 3 O 4 )/wüstite (FeO) layers with varying thickness depending on the oxidation conditions. These oxides were then irradiated with 200 keV, 0.03 dpa protons at room temperature. The oxide microstructure and phase compositions were characterized with transmission electron microscopy (TEM) coupled with electron energy loss spectroscopy (EELS). These results were corroborated with X-Ray diffraction (XRD) and Raman spectroscopy analysis. The relative vacancy concentrations and size distributions in the oxide layers were investigated using positron annihilation spectroscopy (PAS) and positron annihilation lifetime spectroscopy (PALS) techniques. Lastly, these oxides were exposed to a 0.1 M borate buffer solution (pH 9.2) at applied potential where corrosion reactivity was governed by interfacial reactions and ionic defects to regulate the growth processes observed. The potentials were cycled over the ranges where oxides growth and reduction occurred involving Fe/Fe(II)/Fe(III) reactions at a pH which suppressed chemical reactions at the oxide/electrolyte interface and would lead to solubilization of Fe species. The subsequent oxidation, reduction, and semiconductor properties of the oxides were evaluated using AC and DC electrochemical methods, both with and without prior irradiation. Current results demonstrate that radiation damage can manifest itself in the form of vacancy clustering and possible maghemite (γ-Fe 2 O 3 ) formation. These phenomena were corroborated with donor density and diffusivity values calculated using Mott-Schottky analysis and electrochemical impedance spectroscopy (EIS) analysis and equivalent circuit model (ECM) interpretation, respectively. Radiation damages to the outer rate-regulating α-Fe 2 O 3 layer correlates with enhanced anodic current density corresponding to Fe/Fe(II)/Fe(III) reactions. However, proton radiation may also interact with the metal/oxide and oxide/oxide interfaces depending on the oxide structure and H + beam penetration depth, leading to either degradation or improvement in the Fe-oxide corrosion responses. Nevertheless, the damage persists and can continue to impact corrosion mechanisms long after the irradiation source is removed. The multiple techniques adopted, each characterizing a material property of a different length scale (from meso-, micro-, to macroscopic) enable us to hypothesize the roles that point defects played after irradiation and during corrosion and how the radiation-induced changes in the defect characteristics influence corrosion electrochemistry. Acknowledgment Research primarily supported as part of the fundamental understanding of transport under reactor extremes (FUTURE), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Utilization of the Malvern-Panalytical Empyrean diffractometer were supported by Nanoscale Materials Characterization Facility with National Science Foundation under award CHE-2102156. The TEM sample preparation and characterization was performed at the Analytical Instrumentation Facility at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-1542015). LANL is operated by Triad National Security, LLC, for the National Nuclear Security Administration of the U.S. DOE (Contract No. 89233218CNA000001). References [1] R. Soulas, et al., J Mater Sci (2013) 48, 2861–2871. https://doi.org/10.1007/s10853-012-6975-0. [2] J. Han, et al., Corros. Sci. (2021), 186 109456. https://doi.org/10.1016/j.corsci.2021.109456. [3] J. Qiu, et al., Corros. Sci. (2020), 176 109052. https://doi.org/10.1016/j.corsci.2020.109052. [4] J. Wielant, et al., Electrochim. Acta (2007) 52, 7617–7625. https://doi.org/10.1016/j.electacta.2006.12.041. [5] H.L. Chan. et al., (2023) Materialia, 28, 101762. https://doi.org/10.1016/j.mtla.2023.101762.