The present work was produced as part of the MUZIC consortium, a collaboration between a multi-university team from the UK and industrial partners working on the field of nuclear energy, fabrication of alloys and nuclear research. The aim of the project is to establish a multidiscipline mechanistic understanding of the corrosion and breakaway processes of zirconium alloys used as fuel cladding materials in the nuclear industry. A better understanding of the corrosion mechanism of zirconium alloys will not only aid the development of better performing alloys, but will also allow more accurate models to be developed to reliably predict the service life of existing alloys. This could lead to higher burn-up, increase of energy production and reduction of nuclear waste produced.This work seeks to provide a better understanding of the role of residual stresses in the oxide, which are produced during oxidation due to high Pilling-Bedworth ratio and their impact on oxide phase transformation and oxidation kinetics by employing high energy synchrotron X-ray diffraction techniques. This is achieved by observing how stresses change as oxide growth approaches and passes through transition of the corrosion kinetics, their evolution across the oxide thickness, in situ characterising stresses and phase growth early in oxidation process and how stress changes can affect corrosion properties.It was found that relatively high compressive stresses in the two oxide crystal structures are present. The stresses relax with time up to moments before transition where a possible threshold stress magnitude is reached to aid an extensive tetragonal to monoclinic phase transformation. This generalised tetragonal to monoclinic transformation is believed to produce highly stressed monoclinic crystal structure grains and cause defects in the oxide. The above observation is further supported by a decrease of the tetragonal zirconia content. This is the moment that the oxide looses its protective character and a transition of the corrosion kinetics occurs. By comparing different materials it was observed that the minimum magnitude of the tetragonal phase is lower in better performing alloys while the tetragonal content is some cases was relatively low. It is suggested that the amount of the tetragonal phase, in the oxide layer, is not as important as the rate of it transforming into monoclinic. The extent of tetragonal to monoclinic transformation, that introduces defects in the oxide, defines how protective an oxide layer is.The present work provides a contribution to the available knowledge of the importance of residual stresses in the oxide layer and metal substrate of zirconium alloys and how they can affect corrosion rates or act as a precursor to the corrosion transition.
|Date of Award||31 Dec 2012|
- The University of Manchester
|Supervisor||Michael Preuss (Supervisor) & Robert Cottis (Supervisor)|
- Phase fraction
- Residual stress