First principles modelling of oxygen impurities in UN nuclear fuels

We report results of first principles VASP supercell calculations of O impurity in UN fuels placed either at an interstitial tetrahedral position or as a substitution for a host N ion. In the latter case O perfectly fits into N site producing no lattice distortion. Such the O substitutional impurity only slightly affects the formation energies of U and N vacancies nearby. In both interstitial and substitutional positions O atom attracts the additional electron density and transforms into the negatively charged ion. Oxygen incorporation into pre-existing N vacancy is energetically more favourable than into the interstitial position. The O impurities produce an additional peak at the low energy side of N contribution to the DOS calculated for uranium mononitride which could be used for the O identification by means of the UPS spectroscopy. We compare also the DOS calculated for UN and hypothetical isostructural UO. Both O solution and incorporation energies are negative, indicating that O penetration into UN fuel is the energetically favourable. The migration energy of the interstitial O ion is estimated as 2.8 eV.     

Evaluation on chemical state of irradiated rock-like oxide fuels by nuclear and chemical modeling

Chemical forms of fission products in irradiated ROX fuels were calculated by the SOLGASMX-PV code, and the resultant phase equilibrium and the oxygen potential in the fuel were evaluated in order to assess the irradiation behavior of the ROX fuels. For the ROX fuel with reactor grade Pu, the oxygen potential increased to about −140 kJ mol⁻¹ at EOL when all the Pu in the fresh fuel was tetravalent. In the case of fresh fuel which was partially reduced with the [Pu⁺³]/[Pu⁺⁴]=10/90, the oxygen potential increase was suppressed to about −400 kJ mol⁻¹. On the other hand, the oxygen potential of the ROX fuel with weapon grade Pu never exceeded the value of about −400 kJ mol⁻¹. The difference of oxygen potentials was caused by difference of Am amount produced by Pu conversion. The oxygen potential of the irradiated fuel was controlled by the phase equilibria among FPs. The equilibrium between metallic Mo and MoO₂ controlled the oxygen potential to about −400 kJ mol⁻¹.     

Simulation of a gas-cooled fluidized bed nuclear reactor. Part I: Mixed oxide fuels

The worldwide use of enriched uranium has resulted over several decades in a stockpile of ²³⁸U. Fertile ²³⁸U can be converted by nuclear reaction into a transuranic mixture with a fissile content. Fuel which includes a limited proportion of this converted material is already used in some reactors. Use is restricted by the smaller delayed neutron yield and lower negative temperature coefficient of reactivity compared with uranium fuels.     

Enhanced thermal conductivity oxide nuclear fuels by co-sintering with BeO: II. Fuel performance and neutronics

The fuel rod performance and neutronics of enhanced thermal conductivity oxide (ECO) nuclear fuel with BeO have been compared to those of standard UO₂ fuel. The standards of comparison were that the ECO fuel should have the same infinite neutron-multiplication factor k_inf at end of life and provide the same energy extraction per fuel assembly over its lifetime. The BeO displaces some uranium, so equivalence with standard UO₂ fuel was obtained by increasing the burnup and slightly increasing the enrichment. The COPERNIC fuel rod performance code was adapted to account for the effect of BeO on thermal properties. The materials considered were standard UO₂, UO₂ with 4.0 vol.% BeO, and UO₂ with 9.6 vol.% BeO. The smaller amount of BeO was assumed to provide increases in thermal conductivity of 0, 5, or 10%, whereas the larger amount was assumed to provide an increase of 50%. A significant improvement in performance was seen, as evidenced by reduced temperatures, internal rod pressures, and fission gas release, even with modest (5-10%) increases in thermal conductivity. The benefits increased monotonically with increasing thermal conductivity. Improvements in LOCA initialization performance were also seen. A neutronic calculation considered a transition from standard UO₂ fuel to ECO fuel. The calculation indicated that only a small increase in enrichment is required to maintain the k_inf at end of life. The smallness of the change was attributed to the neutron-multiplication reaction of Be with fast neutrons and the moderating effect of BeO. Adoption of ECO fuel was predicted to provide a net reduction in uranium cost. Requirements for industrial hygiene were found to be comparable to those for processing of UO₂.     

Treatment of molten salt wastes by phosphate precipitation: removal of fission product elements after pyrochemical reprocessing of spent nuclear fuels in chloride melts

The removal of fission product elements from molten salt wastes arising from pyrochemical reprocessing of spent nuclear fuels has been investigated. The experiments were conducted in LiCl-KCl eutectic at 550 °C and NaCl-KCl equimolar mixture at 750 °C. The behavior of the following individual elements was investigated: Cs, Mg, Sr, Ba, lanthanides (La to Dy), Zr, Cr, Mo, Mn, Re (to simulate Tc), Fe, Ru, Ni, Cd, Bi and Te. Lithium and sodium phosphates were used as precipitants. The efficiency of the process and the composition of the solid phases formed depend on the melt composition. The distribution coefficients of these elements between chloride melts and precipitates were determined. Some volatile chlorides were produced and rhenium metal was formed by disproportionation. Lithium-free melts favor formation of double phosphates. Some experiments in melts containing several added fission product elements were also conducted to study possible co-precipitation reactions. Rare earth elements and zirconium can be removed from both the systems studied, but alkaline earth metal fission product elements (Sr and Ba) form precipitates only in NaCl-KCl based melts. Essentially the reverse behavior was found with magnesium. Some metals form oxide rather than phosphate precipitates and the behavior of certain elements is solvent dependent. Caesium cannot be removed completely from chloride melts by a phosphate precipitation technique.