| Metal alloy inclusions comprised of Mo, Pd, Rh, Ru, and Tc (the so-called “noble” metals) develop in CANDU fuel pellets as a result of fission. The thermochemical behaviour of this alloy system during severe accident conditions is of interest in connection with computations of loss of volatile compounds of these elements by reaction with steam-hydrogen gas mixtures that develop in the system as a result of water reacting with the Zircalloy cladding.; This treatment focuses on the development of thermodynamic models for the Mo-Pd-Rh-Ru-Tc quinary system. A reasonable prediction was made by modelling the ten binary phase diagrams, five of these evaluations being original to this work. This process provides a complete treatment for the five solution phases (vapour, liquid, bcc-solid, fcc-solid, and cph-solid) in this alloy system, as well as self-consistent Gibbs energies of formation for the Mo 5Ru3 intermetallic phase, and two intermediate phases in the Mo-Tc system. The resulting collection of properties, when treated by Gibbs energy minimization, permits phase equilibria to be computed for specified temperatures and compositions.; Experimental work in support of this treatment has been performed. Measurements of the solidus and liquidus temperatures for Pd-Rh alloys were made using differential thermal analysis. These measurements confirm that the liquid solution exhibits positive deviation from Raoult's law. Experimental work as a visiting research engineer at AECL (Chalk River) was performed using a custom developed Knudsen cell/mass spectrometer. The Pd partial pressure was measured above multi-component alloys of known composition over a range of temperatures. These are correlated to predicted activities of Pd from the developed thermodynamic model in the multi-component alloy.; The thermodynamic treatment developed for the noble metal alloy inclusions has been combined with considerable other data and applied to selected loss-of-coolant-accident scenarios to demonstrate the value of the improved alloy treatment. An original method of compressing voluminous data generated by extensive calculations (as undertaken previously by the author involving an ideal alloy model) is outlined. This technique permits the output from the thermodynamic computations with the models to be incorporated within the fission product release code. |
