Development of an Electrochemical Impedance Instrument for Monitoring Corrosion Formation (Oxide and Hydride) on Cladding Materials
The objective of this work package is to develop electrochemical impedance spectroscopic (EIS) techniques for the in pile measurement of changes in cladding materials in coupling with model simulation and material characterization. This work package will involve the initial development of electrochemical sensing technologies for measuring spatial and time resolved changes in cladding chemistry. Specific attention will be paid to monitoring changes in monitor cladding corrosion including oxide and hydride formation and deformation. The planned work during this period was focused on cladding material zirconium alloy corrosion, oxide and hydride development, and to characterize samples using EIS under controlled gas atmosphere, atom probe tomography (APT), Raman Spectroscopy, and Synchrotron X-ray diffraction (XRD). The corrosion, including oxide and hydride of zirconium alloy samples, was tested in this study. The samples were treated at a gas environment containing 3% H2 (vol%) balanced with N2 gas at various temperatures (100 – 500°C) and different times (up to 60 hours) and were characterized by in situ EIS. After treatment, various characterization techniques were applied to measure the samples, including TGA, Ramen, XRD, and APT. This study found that impedance spectra can be affected significantly with (furnace/environment) temperature. Higher temperature resulted in higher overall impedance, and longer exposure time exerted similar effects. Proof of concept characterization of oxidized samples, including TGA, Raman, XRD, and APT, were accomplished on samples exposed to 700 oC gas environment containing 20% O2 and 80% N2. TGA provides observable breakaway and bulk oxide growth measurements. High-temperature, in-situ Raman provides observation of oxidation stress at the surface of the oxide. Additionally, a transition from tetragonal to monoclinic zirconia can be seen early in the oxidation experiment. Specifically, tetragonal-rich zirconia is seen at the metal/oxide interface, where a transition to monoclinic-rich zirconia is seen in the bulk of the oxide. It has also been confirmed that highly compressive residual stresses are seen near the metal/oxide interface. It is concluded that the transition from tetragonal to monoclinic zirconia is induced by massive shifts in stress as the oxide grows. APT has supplied evident differences in the distribution of zirconium and oxygen at the metal/oxide interface. On the pre-breakaway sample, the metastable Zr(O) region at the boundary is relatively thin, interfaced by Zr-rich (i.e., metal) and O-rich (i.e., ZrO2) on either side. In contrast, it has been seen on a post-breakaway sample that the Zr(O) metastable region is much greater in thickness, with evidence of four “zones” showing slightly contrasting composition between 49-54% Zr. In addition, it can be seen from the Zr-2.65Nb post-breakaway sample that secondary element concentrations are considerably different than bulk composition measurements show. Specifically, Nb concentration is much lower than expected, whereas Fe concentration is much higher than expected. These differences could play a role in each element’s contribution to oxide growth mechanisms, as well as causation for breakaway. Future work is focused on analyzing EIS spectra of hydride and its correlation with characterization features, finite element (FE) modeling of cladding materials, electrochemical sensor development, targeting cladding oxides/hydrides under thermodynamic equilibria, during transients and under irradiation.
- Research Organization:
- Idaho National Lab. (INL), Idaho Falls, ID (United States)
- Sponsoring Organization:
- US DOE Office of Nuclear Energy
- DOE Contract Number:
- DE-AC07-05ID14517
- OSTI ID:
- 1605005
- Report Number(s):
- INL/EXT-19-53207-Rev000
- Country of Publication:
- United States
- Language:
- English
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