Radiation induced dissolution of UO2 based nuclear fuel – A critical review of predictive modelling approaches

Radiation induced dissolution of uranium dioxide (UO₂) nuclear fuel and the consequent release of radionuclides to intruding groundwater are key-processes in the safety analysis of future deep geological repositories for spent nuclear fuel. For several decades, these processes have been studied experimentally using both spent fuel and various types of simulated spent fuels. The latter have been employed since it is difficult to draw mechanistic conclusions from real spent nuclear fuel experiments. Several predictive modelling approaches have been developed over the last two decades. These models are largely based on experimental observations. In this work we have performed a critical review of the modelling approaches developed based on the large body of chemical and electrochemical experimental data. The main conclusions are: (1) the use of measured interfacial rate constants give results in generally good agreement with experimental results compared to simulations where homogeneous rate constants are used; (2) the use of spatial dose rate distributions is particularly important when simulating the behaviour over short time periods; and (3) the steady-state approach (the rate of oxidant consumption is equal to the rate of oxidant production) provides a simple but fairly accurate alternative, but errors in the reaction mechanism and in the kinetic parameters used may not be revealed by simple benchmarking. It is essential to use experimentally determined rate constants and verified reaction mechanisms, irrespective of whether the approach is chemical or electrochemical.     

Effect of metal ions in a heated nitric acid solution on the corrosion behavior of a titanium–5% tantalum alloy in the hot nitric acid condensate

For evaluating the application of titanium and its alloys as components of equipment for storing nitric acid condensate in spent nuclear fuel reprocessing plants, the corrosion behavior of titanium–5% tantalum alloy (Ti–5Ta) in a continuously renewed hot nitric acid condensate, and particularly the effect of metal ions in the heated nitric acid solution, was investigated. Corrosion experiments in an apparatus designed to renew the condensate at regular intervals showed that the corrosion rate of Ti–5Ta in the condensate increased linearly with the nitric acid concentration. The surface morphology of Ti–5Ta coupons after the corrosion experiments indicated uniform corrosion under any condition. The oxide film on the coupons had nearly constant thickness, and it was composed of mainly lower Ti oxides, such as TiO and Ti₂O₃, regardless of the nitric acid concentration in the condensate. The experimental results also showed that the addition of metal ions into the heated nitric acid solution increased the nitric acid concentration in the condensate, which resulted in a higher corrosion rate of Ti–5Ta. The corrosion rate increased noticeably as the valence of the metal ion increased and its ionic radius decreased. This effect of metal ions in the heated nitric acid solution on the corrosion rate of Ti–5Ta in the condensate was evaluated quantitatively based on the Gibbs free energy of hydration of the metal ions, and the calculated corrosion rates of Ti–5Ta in the condensate were found to be in good agreement with the experimental values.     

The solution and diffusion of ruthenium in UO2±x

Atomic scale computer simulation is used to develop models that describe the behaviour of ruthenium in the uranium dioxide lattice. Results are consistent with observed metal particle formation in UO_2−x and UO₂. Conversely it is predicted that ruthenium can be soluble in UO_2+x although in irradiated fuel the extent of ruthenium solution will depend on the total concentration of fission products compared to the oxygen interstitial ion concentration. Second phase oxide particles such as BaRuO₃ and RuO₂ are not predicted to be stable. At all stoichiometries activation energies for migration are high.     

Degradation of UN and UN–U3Si2 pellets in steam environment

In this work, a systematic study of the degradation of UN pellets (density range 96%–99.9% and grain size of 6–24 µm) and UN-10%U₃Si₂ (wt%) composite in a steam environment is presented. Static steam autoclave tests were performed at 300 °C and 9 MPa for period of 0.5–1.5 hours. Microstructural analyses of UN pellets show that, in a high-pressure atmosphere, the fuel collapses principally by intergranular cracking generated by the precipitation of an oxide phase in the grain boundaries. This mechanism leads to a premature mechanical collapse of the fuel pellet, exposing fresh surfaces to steam, and ultimately accelerating the oxidation process. Increasing density (specifically eliminating open porosity) was found to delay the oxidation process, while increasing grain size was found to accelerate the degradation process due to a greater susceptibility to mechanical fracture by way of intergranular oxidation. The performance of the UN-10%U₃Si₂ composite proved to be better when compared to UN. The U₃Si₂ phase served to stabilize the UN grain boundary interface and reacted preferentially with the steam, thereby altering the failure mechanism. In this composite material, the cracking was predominantly intra-granular and the exposure of fresh surfaces was limited, resulting in a slower degradation process.     

Synergistic extraction of U（VI） and Th（IV） from nitric acid media with HBMPPT and TBP in toluene

The sysnergistic extraction of U(VI)and Th(IV) from nitric acid solution by HBMPPT(4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione) and TBP( tributylphosphate)in toluene was studied.The extraction ability of HBMPPT for U(VI) and Th(IV) was not so high.but when a little TBP was added in,the ability to extract U(VI) and Th(IV) was improved.The extracted complexes may be presented as UO2NO3.BMPPT.TBP and UO2(BMPPT)2.TBP for U(VI).and Th(NO3)3.BMPPT.TBP and Th(NO3)2(BMPPT)2.TBP for Th(IV),respectively,in the synergistic extraction system.The synergistic effect of HBMPPT and TBP makes the separation cofeeicient of U(VI)/Th (IV) or U(VI)/Eu(Ⅲ) reach a high value.     

Effects of α-radiation on a direct disposal system for spent nuclear fuel – (2) review of research into safety assessments of direct disposal of spent nuclear fuel in Europe and North America

The Japanese geological disposal programme has started researching disposal of spent nuclear fuel (SF) in deep geological strata (hereafter “direct disposal of SF”) as an alternative management option other than reprocessing followed by vitrification and deep geological disposal of high-level radioactive waste (HLW). In the case of direct disposal of SF, the radioactivity of the waste is higher and the potential effects of the radiation are greater. Specific examples of the possible effects of radiation include: increased amounts of canister corrosion; generation of oxidizing chemical species in conjunction with radiation degradation of groundwater and accompanying oxidation of reducing groundwater; and increase in the dissolution rate and the solubility of SF. Therefore, the influences of radiation, which are not expected to be significant in the case of geological disposal of vitrified waste, must be considered in safety assessments for direct disposal of SF. Focusing especially on the effects of α-radiation in safety assessment, this study has reviewed safety assessments in countries other than Japan that are planning direct disposal of SF. The review has identified issues relevant to safety assessment for the direct disposal of SF in Japan.     

Leaching behavior of gamma-emitting fission products and Np from neutron-irradiated UO2–ZrO2 solid solutions in non-filtered surface seawater

The gamma ray radionuclides Cs-137, Ba-140, I-131, Ce-141, Ru-103, Zr-95, and Np-239 were produced by neutron irradiation of UO₂–ZrO₂ solid solutions that were synthesized as simulated fuel debris under reducing and oxidizing conditions. The leaching ratio of radionuclides was investigated under atmospheric conditions at 25 °C for non-filtered natural surface seawater, as well as deionized water after filtration with a membrane of 0.45-µm pore size or that of nominal molecular weight limit of 3 kDa. The uranium molar concentration was affected by the oxidation state in the solid solution samples. The congruent dissolution of Cs, I, and Ba with the hexavalent uranium of U₃O₈ was facilitated in the seawater samples, whereas a lower leaching ratio of nuclides was observed in the deionized water samples. Neptunium-239, originally produced from uranium-238 in U₃O₈, showed behavior that was similar to that of Cs, I, and Ba. However, the dissolution of Np (as a parent nuclide of Pu-239) in the debris of UO₂ and UO₂–ZrO₂ was suppressed in the same manner as Zr(IV) and Ce(IV). The concentration exhibited no filtration dependence after 15 d, which shows that most of the leached nuclides can exist in their ionic form in seawater.     

Solvent extraction of uranium（VI） and thorium（IV） in nitric acid solution by N,N,N‘,N’—tetrabutyladipicamide

N,N,N‘N‘-tetrabutyladipicamide(TBAA) has been synthesized,and applied to the extraction of U(VI) and Th(IV) from nitric acid solutions in a diluent composed of 0.50 volume fraction 1,2,4-trimethyl benzene (TMA) and 0.50 volume fraction kerosene(OK),The effects of the aueous nitric acid concentration,extractant concentration,slating-out agent (LiNO3) and temperature on extraction ability of TBAA for U(VI) and Th(IV) have been studied.Back Extraction of U(VI) and Th (IV) from organic phases were performed by dilute nitric acid.The compositions of extracted complexes,equilibrium constants and enthalpies of extraction reactions have also been estimated.The IR spectra of extraction of U(VI) and Th(IV) have been studied.     

Effect of metal ion location in reaction medium on formation process and structure of PtCu–CuO nanoparticles supported on carbon and γ-Fe2O3

The process of nanoparticle formation by radiochemical synthesis in a heterogeneous system has been investigated considering the effects of the metal ion location in the reaction medium. PtCu nanoparticles supported on carbon and γ-Fe₂O₃ were synthesized using a high-energy electron beam. The metal ions in the precursor were categorized as those dissolved in solution, adsorbed on support, and precipitated. The ratio of metal ions in the solution was varied prior to the electron beam irradiation and its effects on the synthesized particle structures were examined. The nanoparticles were characterized by inductively coupled plasma-atomic emission spectrometry, transmission electron microscopy, X-ray diffraction, and X-ray absorption spectroscopy. A PtCu alloy and CuO were immobilized on the support in all the samples. The PtCu alloy nanoparticle composition depended on the Cu ion content in the solution. The nanoparticle formation mechanism could be explained using the obtained results. Metal ions present in the solution resulted in formation of the alloy. The adsorbed ions also contributed to the alloy formation by desorbing from the support when irradiated. On the other hand, alloy formation with Pt from the precipitated Cu ions was found to be difficult.