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Mechanisms of Oxidation of Fuel Cladding Alloys Revealed by High Resolution APT, TEM and SIMS Analysis

Published online by Cambridge University Press:  30 March 2012

Chris R. M. Grovenor ,
Na Ni ,
Daniel Hudson ,
Sean S. Yardley ,
Katie L. Moore ,
George D. W. Smith ,
Sergio Lozano-Perez  and
John M. Sykes
Chris R. M. Grovenor
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
Na Ni
Affiliation:
Department of Materials, Imperial College, London, Exhibition Road, London, SW7 2AZ, UK
Daniel Hudson
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
Sean S. Yardley
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
Katie L. Moore
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
George D. W. Smith
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
Sergio Lozano-Perez
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
John M. Sykes
Affiliation:
Department of Materials, Oxford University, Parks Road, Oxford, OX1 3PH, UK
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Abstract

Aqueous corrosion of zirconium alloys has become the major factor limiting prolonged fuel campaigns in nuclear plant. Studies using SEM, TEM and electrochemical impedance measurements have been interpreted as showing a dense inner-most oxide layer, and an increased thickness of the layer has been correlated to a better corrosion resistance. Many authors have reported that an ‘intermediate layer’ at the metal oxide interface has a complex structure or/and stochiometry different to that of both the bulk oxide and bulk metal, sometimes claimed to be a suboxide phase. Diffraction evidence has suggested the presence of both cubic ZrO and rhombohedral Zr3O phases, and compositional analysis has revealed similar variations in local oxygen stoichiometry.

We have carried out a systematic investigation of the structure and chemistry of the metal/oxide interface in samples of commercial ZIRLO corroded for times up to 180 days. We have developed new experimental techniques for the study of these interfaces both by Electron Energy Loss Spectroscopy (EELS) analysis in the Transmission Electron Microscope (TEM) and by Atom Probe Tomography (APT), and exactly the same samples have been investigated by both techniques. Our results show the development of a clearly defined suboxide layer of stoichiometry close to ZrO, and the subsequent disappearance of this layer at the first of the characteristic ‘breakaway’ transitions in the oxidation kinetics. We can correlate this behaviour with changes in the structure of the oxide layer, and particularly the development of interconnected porosity that links the corroding interface with the aqueous environment. Using high resolution SIMS analysis of isotopically spiked samples we demonstrate the penetration of the oxidising species through these porous outer oxide layers.

Keywords

Zroxidationtransmission electron microscopy (TEM)
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1383: Symposium A – Material Challenges in Current and Future Nuclear Technologies , 2012 , mrsf11-1383-a07-05
Copyright
Copyright © Materials Research Society 2012

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References

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