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The Radiolysis of Water over Plutonium Oxide: The Mystery of the Disappearing Oxygen

  • Full or part time
  • Application Deadline
    Sunday, September 15, 2019
  • Funded PhD Project (European/UK Students Only)
    Funded PhD Project (European/UK Students Only)

Project Description

Approximately 138 tonnes of separated Pu is in long term storage at Sellafield as PuO2 powder in nested, sealed steel storage cans. Under certain circumstances, gas generation may occur with consequent storage package pressurisation. In practice, this is rarely seen and empirically derived criteria are used to account for the release of known gases into the package and so ensure safe storage conditions. The purpose of this proposed PhD project is to contribute to a fundamental understanding of the factors influencing the empirical criteria.
There are a number of fundamental mechanisms that could lead to pressurisation, and all must be understood. The 5 main routes suggested are:
(i) Helium accumulation from α decay;
(ii) Decomposition of polymeric packing material;
(iii) Steam produced by H2O desorption from hygroscopic PuO2 due to self-heating or loss of cooling in stores;
(iv) Radiolysis of adsorbed water to generate gaseous hydrogen and oxygen; and,
(v) Generation of H2 by a postulated (hydrothermal) chemical reaction of PuO2 with H2O.
The scope for this PhD is focussed on mechanisms (iv) and (v). Experience has shown that cans sealed under non-ideal conditions can have headspace atmospheres that are hydrogen rich but contain no oxygen.
Small scale studies of PuO2 packages suggest that gaseous hydrogen and oxygen may be formed in such packages. However, these studies also found that the pressure is limited by a H2/O2 recombination process. This may be through a gas phase recombination process of molecular hydrogen and oxygen and could be thermally or radiolytically driven processes.
Preliminary studies indicate that irradiation of gas phase mixtures of hydrogen and oxygen with helium ions or gamma rays can lead to loss of hydrogen, presumably through radiation-induced reaction with oxygen to form water. This loss of hydrogen is found to be accelerated by the presence of zirconium and cerium oxides. The potential role of metal oxide surfaces in promoting this reaction is not clear.
If the hydrogen is produced primarily by the radiolysis of water the comparative absence of oxygen in the can headspace raises questions as to whether this is due to the formation of a suggested PuO2+x phase or some other oxidative process or H2/O2 recombination. Recombination, with or without PuO2 acting as a catalyst, could prevent the coincident observation of the two gases and limit the extent of package pressurisation, but not fully explain why a number of packages have been shown to contain hydrogen.
Thus, questions arise as to whether this putative recombination catalysis exists on PuO2 and the fate of the oxygen. Sellafield Ltd have started a programme of work at NNL to investigate this. The proposed PhD, which will involve a significant period of placement at NNL’s Central Laboratory, will be working to address these questions. The student will work alongside NNL to further the understanding of the efficacy of PuO2 as a catalyst, and understand dependencies of the composition of the gas-phase on the surface activity of the metal oxide.
Parallel/preliminary work at the University will focus on method development for the on-line sampling of both hydrogen and oxygen and potentially other species as a function of T, P, water content, dose rate, specific surface area, co-adsorbed species etc. during recombination / catalytic reaction studies.
The project is intellectually challenging and involves well-integrated elements of chemistry, engineering and materials science. The successful applicant will become familiar with techniques needed to tackle major problems in the nuclear industry and be part of a well-established team of nuclear researchers within Lancaster’s Engineering Department that seeks to address industrial problems while maintaining a strong science and technology base.
Entry requirements
Applicants should have a First or Upper Second Class UK honours degree, or equivalent, in a relevant subject such as chemical engineering, nuclear engineering, materials science, chemistry, radiochemistry or related disciplines.

Funding Notes

Supported by the Nuclear Decommissioning Authority (NDA) through the EPSRC TRANSCEND Consortium (TRANSformative SCience & Engineering for Nuclear Decommissioning), this studentship is available to start 1st October 2019. For UK and EU applicants the studentship is fully funded for 4 years, covering fees and a maintenance grant (£17,009) (all tax free).

For further information:
Professor Colin Boxall , Tel: +44 (0) 1524 593109 or +44 (0) 781 405 5964
Please include CV.

To apply for a PhD at Lancaster University use the on-line application form at:
View Website
You should address your background and suitability for this project in your statement.

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