Oxidation behavior of ferritic-martensitic and ODS steels in supercritical water

Open Access
Bischoff, Jeremy
Graduate Program:
Nuclear Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
May 31, 2011
Committee Members:
  • Arthur T. Motta, Committee Chair
  • Kenan Unlu, Committee Member
  • Paul R. Howell, Committee Member
  • Elizabeth C. Dickey, Committee Member
  • Robert J. Comstock, Committee Member
  • Todd Allen, Committee Member
  • ODS
  • martensitic
  • ferritic
  • steels
  • corrosion
  • supercritical water
  • steam
  • oxide
Ferritic-martensitic and ODS alloys are primary candidates for application as cladding and structural material in Generation IV nuclear power plants, especially the supercritical water reactor. One of the main in-service degradation mechanisms for these alloys is uniform corrosion, thus this project focuses on understanding the oxidation behavior of these alloys in the supercritical water (SCW) environment. This understanding is acquired through the analysis of the oxide microstructure using microbeam synchrotron radiation diffraction and fluorescence associated with electron microscopy (both SEM and TEM). The microbeam synchrotron radiation diffraction and fluorescence technique provides unique microstructural data of the oxide. This technique simultaneously probes elemental and phase information step by step with a sub-micron spatial resolution throughout the oxide layers. Thus we were able to locate specific phases, such as Cr2O3, at specific locations in the oxide layer, mainly the interfaces. The electron microscopy complemented this analysis by imaging the oxide layers, to yield detailed information on the oxide morphology. All the alloys studied exhibited the same three-layer structure with an outer layer containing only Fe3O4, an inner layer containing a mixture of Fe3O4 and FeCr2O4, and a diffusion layer containing a mixture of chromium-rich precipitates (Cr2O3 and FeCr2O4) and metal grains. By analyzing samples with various exposure times, we were able to follow the evolution of the oxide microstructure with exposure time. To obtain the corroded samples, several corrosion experiments were performed: some in supercritical water (at 500°C and 600°C) and one experiment in 500°C steam. The test in steam was undertaken to obtain more data points in the kinetic curves, because we thought the corrosion in steam and supercritical water at the same temperature would result in similar kinetics. This turned out not to be the case and the samples in supercritical water corroded much faster than those in steam (1.5 to 2 times faster). Additionally, during these corrosion tests a marker experiment was performed with the deposition of micrometric palladium markers on the surface of some samples prior to oxidation. The markers were found at the outer-inner layer interface, consistent with a corrosion mechanism of outward migration of iron to form the outer layer and inward migration of oxygen to form the inner layer. The discrepancy between the SCW and steam environments suggests that the outward migration of iron may be the rate-limiting step. A detailed study of the oxide advancement was performed using the TEM by analyzing the inner and diffusion layer structure. Energy-filtered TEM images were acquired to analyze the micrometric and nanometric distribution of elements in these layers. Such images from the inner layer revealed the presence of localized chromium enrichment regions associated with the presence of pores. Additionally, an iron-chromium nanometric segregation was observed and may be associated with the mixture of Fe3O4 and FeCr2O4. In the diffusion layer, small nanometric chromium-rich oxide particles were seen within metal grains. The (Fe,Cr)3O4 spinel oxide has an inverse spinel structure as Fe3O4 but becomes normal spinel as FeCr2O4, thus the structure changes depending on the chromium content. Additionally, the spinel structure was analyzed using the ligand theory and showed that chromium does not migrate and that the main diffusing species is the Fe2+ ion. Calculations of the amount of iron leaving the inner layer showed that this amount accounted for the amount of iron necessary to form the outer layer, thus no dissolution of oxide in SCW is observed. Additionally, the differences in oxidation behavior in steam and SCW suggest that the rate-limiting step for the corrosion of ferritic-martensitic steels is the iron outward migration. The iron migration is driven by the gradient in the Fe2+/Fe3+ ratio and is associated with a flux of vacancies in the opposite direction. The vacancies coalesce into pores at the inner-diffusion layer interface. These results are presented and discussed in this thesis and were used to analyze the oxidation behavior of ferritic-martensitic and ODS alloys in SCW. Finally, a mechanism of oxide advancement is proposed.