Equilibrium and nonequilibrium molecular dynamics simulations of heat conduction in uranium oxide and mixed uranium-plutonium oxide

The thermal conductivity of nuclear fuels such as UO_2+x and (U,Pu)O_2−x has been calculated by the molecular dynamics (MD) simulation in terms of oxygen stoichiometric parameter x, temperature and Pu content. In the present study, the MD calculations were carried out in both equilibrium (EMD) and nonequilibrium (NEMD) systems. In the EMD simulation, the thermal conductivity was defined as the time-integral of the correlation function of heat fluxes according to the Green-Kubo relationship. Meanwhile, in the homogeneous NEMD, it was given by the ratio of the time-averaged heat flux to the perturbed external force subjected to each particle in the simulated cell. NEMD, as compared with EMD, gave somewhat precise results efficiently. Furthermore, both MD calculations showed that the thermal conductivity of these oxide fuels decreased with increase of temperature and defects, i.e. excess oxygen or vacancy, and was rather insensitive to Pu content for the stoichiometric fuel.     

Some equilibria in the uranium-plutonium-nitrogen ternary system. An assessment

Some assessments of possible equilibria for the ternary system uranium-plutonium-nitrogen have been made and from these equilibria the pressures of the gas phase species. Pu, U and N₂ for the system have been calculated. The nature of the vaporization behaviour of alloys of the system is also predicted.     

Structural studies of the phase separation in the UO2–PuO2–Pu2O3 ternary system

In the oxygen hypo-stoichiometric range of (U_1?yPu_y)O_2?x mixed oxide MOX fuels, the U–Pu–O phase diagram is known to exhibit a large biphasic domain depending on the Pu content. However, the phase equilibria are still to be fully described as various representations are proposed in the literature.In the present work, we notify new insights into the phase separation occurring in the UO₂–PuO₂–Pu₂O₃ domain at room temperature. Our microstructural and X-ray diffraction results are compared to the different representations reported in the literature. We provide, for the first time in the hypo-stoichiometric domain, an indisputable experimental observation of a triphasic region at high Pu content, composed of two fluorite-type structures and of one α-Pu₂O₃ sesquioxyde type structure. These results are in contradiction with previous experimental representations of the U–Pu–O ternary system.     

Swelling analysis of highly-rated MX-type LMFBR fuels: II. Microsopic swelling behaviour

Microscopic swelling has been investigated by electron microscopy in several MX-type fuels, irradiated in fast and thermal flux. The results show that fission gas bubbles in these compounds grow to large sizes if the in-pile temperature rises above a critical value (swelling critical temperature $\text{T}{}_{\mathrm{c}}$). A comparison has been made of the swelling rates in fuels of different composition, showing that $\text{T}{}_{\mathrm{c}}$ increases from carbides to nitrides. In fuels subjected to in-pile restructuring (highly rated He-bonded pins) microscopic swelling is affected by pore and grain boundary migration. The influence of these phenomena on the fuel swelling performance has been discussed.     

Research and Development of Minor Actinide-containing Fuel and Target in a Future Integrated Closed Cycle System

Research and development of minor actinide-containing fuels and targets, i.e., (Pu,Am)O₂–MgO, (Pu,Np)O₂–MgO, (U,Pu,Np)O₂, (U,Pu,Np)N and (Pu,Np,Zr)N, for use in a future integrated closed cycle system that includes fast reactor and accelerator driven sub-critical system is underway. The present statuses of fabrication test and property measurements are given. Design concept of the oxide target is described in detail together with a screening of the support material. A new apparatus for the measurement of mechanical properties at the elevated temperature is installed for use in evaluating the fuel-cladding mechanical interaction. Development histories with future prospects of two types of Np-containing fuels for the fast reactor are mentioned. Preliminary test results for a new nitride target for the accelerator driven sub-critical system are given. Finally, an irradiation test plan in the experimental fast reactor JOYO is briefly described.     

Phase diagram analysis of (U,Pu)O2−x sub-system

The high plutonium, hypo-stoichiometric fuel exists as two phase system at low temperatures. The partial phase diagram of (U,Pu)O_2−x with two coexisting cubic phases was extensively investigated in this work using theoretical models. The critical temperature of the miscibility gap varies with Pu/M and O/M of the system. Based on the similar miscibility gap behaviour observed in PuO_2−x system and the experimental data available on the phase boundaries of (U,Pu)O_2−x for various Pu/M, some semi-empirical relationships and solution models were developed. With the help of these relationships, ternary isothermal sections of the miscibility gap, O/M at different temperatures and the critical temperature of the miscibility gap of (U,Pu)_2−x for different Pu/M values were calculated. These calculated values were compared with the available literature data.     

Application of fluoride volatility method to the spent fuel reprocessing

ABSTRACT

An advanced reprocessing system has been developed to treat various SF (spent fuels): spent UO₂ and MOX (mixed oxide) fuels from LWR (light water reactor) and MOX fuel from FR (fast reactor). The system consists of SF fluorination to separate most U (uranium) as volatile UF₆, dissolution of solid residue containing Pu (plutonium), FP (fission products), MA (minor actinides) and partial U by nitric acid, and Pu+U separation from FP and MA by conventional solvent extraction. Gaseous UF₆ is purified by the thermal decomposition and the adsorption of volatile PuF₆ and adsorption of other impurities. This system is a hybrid process of fluoride volatility and solvent extraction and called FLUOREX. Fluorination of most U in the early stage of the reprocessing process is aimed at sharply reducing the amount of SF to be treated in the downstream aqueous steps and directly providing purified UF₆ for the enrichment process without conversion. The FLUOREX can flexibly adjust the Pu/U ratio, rapidly separate UF₆ and economically treat aqueous Pu+U. These features are especially suitable for the transition period fuel cycle from LWR to FR. This paper summarizes the feasibility confirmation results of FLUOREX.     

Reactions of Uranium-Plutonium Alloys with Iron

In metallic U-Pu-Zr fuel for fast reactors, metallurgical reactions occur between the fuel alloy and the stainless steel cladding, and a liquid phase may be formed in the reaction zone at a higher temperature. In order to clarify the condition for liquefaction at the fuel-cladding interface, the reactions of U-Pu alloys with Fe have been examined at 923 and 943 K. The test results confirmed that the liquid phase is not formed at 923 K in any region of the reaction zone when the maximum Pu content in the (U,Pu)₆Fe phase is less than the Pu solubility limit in this phase. Comparison of the present test results with the liquefaction data from the various tests on metallic fuel-cladding compatibility suggested that the liquefaction condition is independent of the Zr content in the fuel alloy and can be expressed as a function of the atom fraction ratio of Pu/(U+Pu) in the fuel alloy and the reaction temperature. At 923 K, liquefaction will occur when the Pu/(U+Pu) ratio is larger than 0.25.     

Inherent Protection of Plutonium by Doping Minor Actinide in Thermal Neutron Spectra

The present study focuses on the exploration of the effect of minor actinide (MA) addition into uranium oxide fuels of different enrichment (5% ²³⁵U and 20% ²³⁵U) as ways of increasing fraction of even-mass-number plutonium isotopes. Among plutonium isotopes, ²³⁸Pu, ²⁴⁰Pu and ²⁴²Pu have the characteristics of relatively high decay heat and spontaneous fission neutron rate that can improve proliferation-resistant properties of a plutonium composition. Two doping options were proposed, i.e. doping of all MA elements (Np, Am and Cm) and doping of only Np to observe their effect on plutonium proliferation-resistant properties. Pressurized water reactor geometry has been chosen for fuels irradiation environment where irradiation has been extended beyond critical to explore the subcritical system potential. Results indicate that a large amount of MA doping within subcritical operation highly improves the proliferation-resistant properties of the plutonium with high total plutonium production. Doping of 1% MA or Np into 5% ²³⁵U enriched uranium fuel appears possible for critical operation of the current commercial light water reactor with reasonable improvement in the plutonium proliferation-resistant properties.     

Implementation of an LBE spallation target in an accelerator-driven molten salt subcritical reactor

An accelerator-driven system (ADS) combined with a subcritical molten salt reactor (MSR) is a type of hybrid reactor originally designed to use Th/U (or U/Pu ) fuel cycles. In most accelerator-driven molten salt reactor (AD-MSR) concepts, the salt material is also used as a target for inducing spallation neutrons. Although a neutron source is an important component in the design of ADS, only a few studies have addressed the effects of the neutron spallation source in the AD-MSR. Incidentally, there is no quantitative study on how much the beam power can be reduced by installing a spallation target in a sodium chloride-based fast reactor. We studied the proton and the neutron source efficiencies of an AD-MSR with chloride fuels by considering an Lead Bismuth Eutectic (LBE) spallation target. This LBE target is found to increase the proton source efficiency significantly. The required beam power for an AD-MSR can be reduced by 33 % and 16 % for NaCl-Th/²³³U and NaCl-U/Pu fuels, respectively, relative to the AD-MSR without the LBE spallation target by keeping the same k_eff. The energy gain can be increased up to 1.5 times and 1.2 times for NaCl-Th/²³³U and NaCl-U/Pu fuels, respectively. Thus, incorporating a spallation target module in an AD-MSR can significantly reduce the burden on the accelerator.     

Helium behavior in oxide nuclear fuels: First principles modeling

UO₂ and (U, Pu)O₂ solid solutions (the so-called MOX) nowadays are used as commercial nuclear fuels in many countries. One of the safety issues during the storage of these fuels is related to their self-irradiation that produces and accumulates point defects and helium therein.We present density functional theory (DFT) calculations for UO₂, PuO₂ and MOX containing He atoms in octahedral interstitial positions. In particular, we calculated basic MOX properties and He incorporation energies as functions of Pu concentration within the spin-polarized, generalized gradient approximation (GGA) DFT calculations. We also included the on-site electron correlation corrections using the Hubbard model (in the framework of the so-called DFT + U approach). We found that PuO₂ remains semiconducting with He in the octahedral position while UO₂ requires a specific lattice distortion. Both materials reveal a positive energy for He incorporation, which, therefore, is an exothermic process. The He incorporation energy increases with the Pu concentration in the MOX fuel.     

The influences of Pu and Zr on the melting temperatures of the UO2–PuO2–ZrO2 pseudo-ternary system

Specimens of (U, Pu, Zr)O₂ were prepared as simulated corium debris that were assumed like debris generated in the severe accident of the Fukushima Daiichi Nuclear Power Plant and their melting temperatures were measured by the thermal arrest technique in order to evaluate the influence of plutonium and zirconium content on the melting temperature of the corium debris. From the evaluation, it was found that the influence of zirconium on the melting temperatures of both (U, Pu, Zr)O₂ and (U, Zr)O₂ was similar and that the melting temperature of (U, Pu, Zr)O₂ had a local maximum value in the Pu-content between 0 and 20 mol%. The UO₂–PuO₂–ZrO₂ pseudo-ternary phase diagram at 2900 and 3000 K was evaluated from the present experimental results and previously reported results.     

Vaporization of uranium-carbon-nitrogen system

The vaporization of species from the uranium-carbon-nitrogen system has been investigated by mass spectrometry with the Knudsen cell technique. After calibration with gold, the vapor pressures of U and N₂ have been obtained over UC_1?xN_x in the temperature range of 1900–2300K. For uranium mono-nitride, values of enthalpies Δ$\text{H}$°₂₉₈ for overall reaction (1)$\text{UN(s) = U(g) + 0.5N}{}_2\text{(g)}$ and the partial reactions (2)$\text{UN(s) = U(L) + 0.5N}{}_2\text{(g)}$ and $\text{U(L) = U(g)}$ have been obtained with both second- and third-law treatments. For UC_1?xN_x the experimental vapor pressures were used to calculate activity of UN in the solutions. For three compositions ($\text{x = 0.69}$, 0.48, 0.30) measured, activity coefficients were found to be slightly smaller than unity.     

ECRIX-H experiment: Synthesis of post-irradiation examinations and simulations

The purpose of the ECRIX-H experiment is to study the behaviour of a composite ceramic target made of AmO_1.62 microdispersed in an MgO matrix irradiated for 318 EFPD in the Phenix sodium-cooled fast reactor (SFR), in a specific carrier sub-assembly equipped with annular blocks of CaH_x acting as a neutron moderator. Results indicate that magnesia-based inert matrix targets display satisfactory behaviour and moderate swelling under irradiation, even for significant quantities of helium produced and a high burn-up. On this basis, the design of transmutation fuel pins for recycling of minor actinides (MA) in accelerator-driven systems (ADS) or in fast neutron reactors (FR) could be optimised so as to increase their performance level (initial MA content, burn-up, etc.).The measured Am fission rate (25 at.%) was found to be lower than that predicted by neutronic simulations probably due to the inaccuracies linked to the complexity of neutron modelling and the uncertainties on nuclear data related to moderated neutron spectrum. In addition, as most of the initial Am transmuted into Pu under irradiation, a PuO_x-type phase was created within the initial AmO_1.62 particles, leading to the incomplete dissolution of the irradiated targets under standard reprocessing conditions. This issue will have to be considered and investigated in greater detail for all transmutation fuels and targets devoted to the multi-recycling of MA.     

Determination of fissile fraction in MOX (mixed U + Pu oxides) fuels for different burnup values

When spent Light Water Reactor fuels are processed by the standard Purex method of reprocessing, plutonium (Pu) and uranium (U) in spent fuel are obtained as pure and separate streams. The recovered Pu has a fissile content (consisting of ²³⁹Pu and ²⁴¹Pu) greater than 60% typically (although it mainly depends on discharge burnup of spent fuel). The recovered Pu can be recycled as mixed-oxide (MOX) fuel after being blended with a fertile U makeup in a MOX fabrication plant. The burnup that can be obtained from MOX fuel depends on: (1) isotopic composition of Pu, which is closely related to the discharge burnup of spent fuel from which Pu is recovered; (2) the type of fertile U makeup material used (depleted U, natural U, or recovered U); and (3) fraction of makeup material in the mix (blending ratio), which in turn determines the total fissile fraction of MOX. Using the Non-linear Reactivity Model and the code MONTEBURNS, a step-by-step procedure for computing the total fissile content of MOX is introduced. As was intended, the resulting expression is simple enough for quick/hand calculations of total fissile content of MOX required to reach a desired burnup for a given discharge burnup of spent fuel and for a specified fertile U makeup. In any case, due to non-fissile (parasitic) content of recovered Pu, a greater fissile fraction in MOX than that in fresh U is required to obtain the same burnup as can be obtained by the fresh U fuel.     

The results of the irradiation experiment HELIOS

The HELIOS irradiation experiment is the latest of a series of experiments on americium transmutation, and has been carried out in the framework of EURATOM’s 6th Framework Programme (FP6) project EUROTRANS, which was completed in March 2010. The transmutation of Minor Actinide (MA) is a fundamental step in order to be able to close the cycle of the nuclear fuel. Past experimental activities in the field of transmutation and testing of innovative nuclear fuel containing Am has proved that the release or trapping of helium is a key issue for the design of such kind of fuel or targets. Therefore, the main objective of the HELIOS experiment is the study of the in-pile behaviour of U-free fuels, such as (Pu,Am,Zr,Y)O₂ or (Am,Zr,Y)O₂, CERCER (Am₂Zr₂O₇+MgO), CERMET ((Pu,Am)O₂+Mo) or ((Am,Zr,Y)O₂+Mo), to gain knowledge on the role of the fuel microstructure and of the operating temperature on gas release and fuel swelling.The HELIOS irradiation experiment started in the HFR (High Flux Reactor) in Petten (The Netherlands) on the 29th of April 2010 and finished on the 19th of February after 9 reactor cycles (∼241 full power days). Although the Post-Irradiation Examination (not performed yet) conducted on the CERCER and CERMET target fuel tested during the HELIOS irradiation experiment will determine the performance of the fuel, the behaviour of such targets during the irradiation did not show any difficulties. It is possible to conclude that from an operational point of view, these kinds of fuel targets which have been developed mainly having in mind the possibility to burn MA in a in a subcritical nuclear system, did not show significant issues. This paper summarises the main experimental data obtained during the 9 cycle irradiation of the HELIOS experiment in the HFR.     

Melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O2−x

The melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O_2−x ((Pu,Am)O_2−x-MgO fuels) was experimentally investigated. Heat-treatment tests were carried out at 2173 K, 2373 K and 2573 K each. The fuel melted at about 2573 K in the eutectic reaction of the Pu-Am-Mg-O system. The (Pu,Am)O_2−x grains, MgO grains and pores grew with increasing temperature. In addition, Am-rich oxide phases were formed in the (Pu,Am)O_2−x phase by heat-treatment at high temperatures. The melting behavior was compared with behaviors of PuO_2−x-MgO and AmO_2−x-MgO fuels.     

Releases of Cesium and Poorly Volatile Elements from UO2 and MOX Fuels under Severe Accident Conditions

Radionuclide release from fuel under severe accident conditions has been investigated in the VEGA program at the Japan Atomic Energy Agency. In this program, three types of fuel, two UO₂ fuels irradiated at PWR and BWR and a MOX fuel irradiated at the ATR Fugen, were heated up to about 3130K in helium atmosphere at 0.1 MPa. Comparison of experimental data and evaluation with computer code analyses showed that Cs release is essentially identical among the three fuels. The Cs release from fuel may differ below about 1770K due to a difference in migration to grain boundaries during irradiation. The difference was not also observed for releases of poorly volatile elements, namely, U, Pu, Sr and Mo between UO₂ and MOX fuels. The release rate of Pu became slightly higher than that of U at 3130 K. The release rate of Sr increased at 3130 K, while that of Mo was quite low at temperatures above 2310 K.     

Co-processing of uranium and plutonium for sodium-cooled fast reactor fuel reprocessing by acid split method for plutonium partitioning without reductant

A solvent extraction flowsheet for Pu partitioning, based on the acid split method without reductant, originally proposed by the Oak Ridge National Laboratory (ORNL), was tested for sodium-cooled fast reactor fuel reprocessing. To enhance resistance to nuclear proliferation, a flowsheet for co-processing was developed that controls Pu content in the products while avoiding Pu polymerization and formation of a third phase during extraction. In this method, Pu is partitioned using the difference in distribution coefficients of U and Pu. It is effective for selective Pu stripping from U at low temperatures and HNO₃ concentrations. The flowsheet with a supply of 0.15 mol/dm³ HNO₃ solution at 21°C for Pu partitioning was tested experimentally using miniature centrifugal contactors and a highly radioactive solution. Neither a Pu(IV) polymer nor a third phase was observed during the experiment. The Pu content in the U/Pu product increased to 2.28 times that in the feed solution. The leakage ratio of Pu to the U product was slightly less in the U stripping section. Some fission products (FPs) were effectively decontaminated; e.g., decontamination factors (DFs) of Cs in U/Pu and U products were 4.51×10⁵ and 2.42×10⁵, respectively.