Thermal conductivity degradation analyses of LWR MOX fuel by the quasi-two phase material model

The temperature measurements of mixed oxide (MOX) and UO₂ fuels during irradiation suggested that the thermal conductivity degradation rate of the MOX fuel with burnup should be slower than that of the UO₂ fuel. In order to explain the difference of the degradation rates, the quasi-two phase material model is proposed to assess the thermal conductivity degradation of the MIMAS MOX fuel, which takes into account the Pu agglomerate distributions in the MOX fuel matrix as fabricated. As a result, the quasi-two phase model calculation shows the gradual increase of the difference with burnup and may expect more than 10% higher thermal conductivity values around 75 GWd/t. While these results are not fully suitable for thermal conductivity degradation models implemented by some industrial fuel manufacturers, they are consistent with the results from the irradiation tests and indicate that the inhomogeneity of Pu content in the MOX fuel can be one of the major reasons for the moderation of the thermal conductivity degradation of the MOX fuel.     

Effects of Fuel Oxidation and Dissolution on Volatile Fission Product Release under Severe Accident Conditions

The release of volatile fission products from high-burnup UO₂ fuel was examined in a steam atmosphere under severe accident conditions as a part of the VEGA program. The effects of fuel oxidation and dissolution were totally evaluated, by comparing the results with those from previous inert, hydrogen and steam atmosphere tests. It was shown that the oxidation of UO₂ to UO_2+x by steam generally enhances Cs and Kr release. However, the enhancement becomes smaller above the melting temperature of Zircaloy, about 2030 K, likely due to reduction of UO_2+x by molten Zircaloy. The burst release of Cs occurs above about 2300K in the hydrogen atmosphere, while the release rate does not increase so significantly for the examined temperature range (<2800 K) in the steam atmosphere. Analysis of the hydrogen atmosphere test showed that fuel dissolution is apparently connected with the burst release and that a large fraction of Cs is quickly released from the dissolved fuel above 2300 K. It is considered that the fuel dissolution rate in the steam atmosphere is about 1/1000 of that in the hydrogen atmosphere.     

MOX Fuel Performance Experiment Specified for Japanese PWR Utilisation in the HBWR

In order to obtain high burn-up MOX fuel irradiation performance data, SBR and MIMAS MOX fuel rods with Pufissile enrichment of about 6 wt% have been irradiated in the HBWR. In-pile performance data of MOX have been obtained, and the peak burn-up of MOX pellet have reached to 66 GWd/tM as of October 2004. MOX fuel temperature is confirmed to have no significant difference compared to UO₂, if taking into account adequately for thermal conductivity degradation due to PuO₂ addition and burn-up development, and measured fuel temperature agrees well with HB-FINE code calculation up to high burn-up region. Fission gas release of MOX is possibly larger than UO₂ based on temperature and pressure assessment. No significant difference is confirmed between SBR and MIMAS MOX on FGR behaviour. MOX fuel swelling rate agrees well with solid swelling rate. Cladding elongation data shows onset of PCMI in high power region. Ramp test data from other experiment programs with various types of MOX fabrication route confirms superior PCI resistance of MOX compared to UO₂, due to enhanced creep rate of MOX. The irradiation is expected to continue until achieving of 70 GWd/tM (MOX pellet peak).     

Analysis of measured isotopic compositions by CASMO5 coupled with a JENDL-4.0 base library for irradiated fuel of light water reactors

Measured isotopic compositions of UO₂ and MOX fuel samples taken from irradiated light water reactor fuel assemblies were analyzed by CASMO5 coupled with a JENDL-4.0 base library to assess the uncertainties in the calculated isotopic compositions on heavy and fission product nuclides. The burnup calculations for the analysis were performed based on a single-assembly model taking into account the detail fuel assembly specifications and irradiation histories. For the MOX fuel samples, a multiple-assembly model was also adopted taking into account the effect of the surrounding UO₂ fuel assemblies. The average and standard deviation of the biases (C/E ? 1's (here C and E are calculated and measured results, respectively)) were calculated for each nuclide separately on the PWR and BWR UO₂ fuel samples. The averaged biases for ²³⁵U, ²³⁶U, ²³⁹Pu, ²⁴⁰Pu, ²⁴¹Pu and ²⁴²Pu were 2.7%, ?0.9%, 0.3%, 0.7%, ?2.4% and ?1.7% for PWR UO₂ samples, and 6.7%, ?1.5%, 2.5%, ?0.6%, 0.4% and ?0.1% for BWR UO₂ samples, respectively. The biases with the single-assembly model on the MOX fuel samples showed large positive values of ²³⁹Pu, and application of the multiple-assembly model reduced the biases as reported in our previous studies.     

Analysis of measured isotopic compositions of high-burnup PWR MOX and UO2 fuels in the MALIBU program

The measured isotopic compositions of fuel samples taken from high-burnup spent PWR MOX and UO₂ assemblies in the MALIBU program has been analyzed by lattice physics codes. The measured isotopes were U, Np, Pu, Am, and Cm isotopes and about 30 major fission product nuclides. The codes used in the present study were a continuous-energy Monte Carlo burnup calculation code (MVP-BURN) and a deterministic burnup calculation code (SRAC) based on the collision probability method. A two-dimensional multi-assembly geometrical model (2 × 2 model) was mainly adopted in the analysis in order to include the fuel assemblies adjoining the relevant fuel assembly, from which the samples were taken. For the MOX sample, the 2 × 2 model significantly reduces the deviations of the calculated results from the measurements compared with a single assembly model. The calculation results of MVP-BURN in the 2 × 2 model reproduce the measurements of U, Np, and Pu isotopes within 5% for the MOX sample of 67 GWd/t. The deviations of their calculated results of U, Np, and Pu isotopes from the measurements are less than 7% for the UO₂ sample of 72 GWd/t.     

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.     

ADAGIO technique: From UO2 fuels to MOX fuels

The amount of gas at the grain boundaries plays an important role in the fuel transient behaviour during accident conditions, such as a loss-of-coolant accident (LOCA) or a reactivity-initiated accident (RIA). Direct experimental determination of the grain boundary gas inventory has been performed for MOX fuel irradiated in an EDF pressurised water reactor (PWR) using the ADAGIO technique (ADAGIO is a French acronym meaning ‘Discriminatory Analysis of Accumulated Inter-granular and Occluded Gas’). The ADAGIO protocol applied to a MOX MIMAS fuel produced inter-granular gas fraction results that were consistent with those reached with other methods of evaluation i.e. electron probe microanalysis (EPMA). Furthermore, a new methodology for the numerical treatment of ⁸⁵Kr release kinetics which was developed for UO₂ was applied to MOX fuels. The corresponding results evidenced two types of release kinetics. These kinetics were attributed to the inter-granular bubbles of the UO₂ matrix and the bubbles located in the restructured zones, i.e. Pu agglomerates.     

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.     

Determination of Li-6/Li-7 Isotopic Ratio by Means of Thermogravimetric Analysis for Lithium Sulphate Monohydrate

Plutonium concentrations and burnup at Pu spots were calculated in U-Pu mixed oxide (MOX) fuel pellets for light water reactors with the neutron transport and burnup calculation code VIMBURN. The calculation models were suggested for Pu spots and U matrices in a heterogeneous MOX fuel pellet. The calculated Pu concentrations and burnup at Pu spots were compared with the PIEs data in a MOX pellet (38.8 MWd/kgHM). The calculated Pu concentrations agreed by 5–18% with the measured ones, and the calculated burnup did by less than 10% with the estimated one with the measured Nd concentrations. Commercial PWR types of MOX fuels were also analyzed with the calculation code and the models. Burnup at Pu spot increased as the distance was greater from the radial center of a MOX fuel pellet. Burnup at Pu spots in the peripheral region became 3–5 times higher than pellet average burnup of 40 MWd/kgHM. The diameters (20–100 μm) of Pu spots were not found a significant factor for burnup at Pu spots. In the outer half volume region (outer than r/r _o=0.7) of a MOX fuel pellet, burnup at Pu spots exceeded 70MWd/kgHM (the threshold burnup of microstructure change in UO₂ fuel pellet) at pellet average burnup of 1430 MWd/kgHM.     

Thermal conductivity evaluation of high burnup mixed-oxide (MOX) fuel pellet

The thermal conductivity formula of fuel pellet which contains the effects of burnup and plutonium (Pu) addition was proposed based on the Klemens’ theory and reported thermal conductivities of unirradiated (U, Pu) O₂ and irradiated UO₂ pellets. The thermal conductivity of high burnup MOX pellet was formulated by applying a summation rule between phonon scattering parameters which show the effects of plutonium addition and burnup. Temperature of high burnup MOX fuel was evaluated based on the thermal conductivity integral which was calculated from the above-mentioned thermal conductivity formula. Calculated fuel temperatures were plotted against the linear heat rates of the fuel rods, and were compared with the fuel temperatures measured in a test reactor. Since both values agreed well, it was confirmed that the proposed thermal conductivity formula of MOX pellets is adequate.     

Thermal conductivity of homogeneous and heterogeneous MOX fuel with up to 44 MWd/kgHM burn-up

New thermal diffusivity data for homogeneous SBR and heterogeneous MIMAS and OCOM MOX fuels are reported. No significant difference between the thermal diffusivity of the homogeneous and heterogeneous fuels was found at the burn-up up to 44 MWd/kgHM. These measurements, combined with previously published results or correlation functions for irradiated UO₂ and MOX were compared and it was found that separate correlations for these two fuels are not justified. A correlation for the thermal conductivity of irradiated UO₂ and MOX as a function of burn-up and irradiation temperature is proposed.     

Decrease of Cesium Release from Irradiated UO2 Fuel in Helium Atmosphere under Elevated Pressure of 1.0 MPa at Temperature up to 2,773K

In the case of severe accidents, the radionuclides release from fuel could mostly occur at high temperature under elevated pressure. The effect of temperature on the release has been clarified in many previous studies while the pressure influence has been scarcely investigated so far due to difficulty in the experimental operation. To investigate the effect of pressure on the release, two tests under the same conditions except for the system pressure were performed in the VEGA program at JAERI by heating up the irradiated UO₂fuels up to 2,773 K in inert helium. The test results uniquely showed that the release rate of cesium for the temperatures below 2,773 K at 1.0 MPa could be suppressed by about 30% compared with that at 0.1 MPa. This article describes the outlines of the two tests and the observed effects of system pressure on cesium release as well as the results of various post-irradiation examinations. Moreover, the mechanisms and models that explain the pressure effect are discussed.     

An Apparatus for Continuously Measuring Radon-222 Exhalation from Ground

High burnup MOX and UO₂ test rods were prepared from the fuel rods irradiated in commercial BWRs. Each test rod was equipped with a fuel center thermocouple and reirradiated in the Halden boiling water reactor (HBWR) in Norway. The burnups of MOX and UO₂ test rods reached about 84GWd/tHM and 72GWd/t, respectively. Fuel temperature was measured continuously during the re-irradiation tests. Thermal conductivity change in high burnup fuel was evaluated from the results of comparison between the measured fuel temperature and the data calculated by using the fuel analysis code FEMAXI-6. The comparison results suggested that the thermal conductivity of MOX fuel pellets is comparable to that of UO₂ fuel pellets in the high burnup region around 80 GWd/t. It is probable that the impurity effect of Pu atoms gradually diminishes with increasing burnup because other factors that affect pellet thermal conductivity, such as the accumulation effect of soluble fission products and irradiation-induced defects in crystal lattice, become dominant in a high burnup region.     

Analysis of MOX Fuel Behavior in Halden Reactor by FEMAXI-6 Code

Capabilities of the FEMAXI-6 code to analyze the behavior of high burnup MOX fuels in LWRs have been evaluated. Coolant conditions, detailed power histories and specifications of the MIMAS-MOX fuel rods, rod 10 and rod 11, of IFA-597.4–7 irradiated in the Halden reactor were input, and calculated rod internal pressures and pellet center temperatures were compared with the measured data for the range of 0-31 MWd/kgUO₂. Some sensitivity studies were conducted mainly with respect to pellet thermal conductivity and swelling rate to investigate the changes in thermal behavior and their effects on fission gas release.

In the irradiation period up to about 23 MWd/kgUO₂, the calculated pellet center temperatures sufficiently agreed with the measured data and also the calculated rod internal pressures reproduced the tendency of an increase in the measured rod internal pressures. These results suggest that fission gas release from MOX fuels can be reasonably predicted by a diffusion process that is modeled in UO₂ pellet grains. On the other hand, the steep increase in the measured rod internal pressures observed at the power ramp around 23 MWd/kgUO₂ cannot be reproduced by FEMAXI-6 and can be regarded as the result of a relatively large amount of gas release, which possibly caused a pellet-cladding-gap closure through pellet gas-bubble swelling.     

Modeling and parametric studies of the effect of inhomogeneity on fission gas release in LWR MOX fuel

To analyze the effect of an inhomogeneous mixture of an PuO₂ powder on fission gas release in MOX fuel, a model has been developed using the assumption that gas release mechanism in Pu-rich particles is identical with that in UO₂ fuel. A parametric study was performed to see the respective effect of the number density, size and fraction of Pu retained in the Pu-rich particles on gas release in MOX fuel. The model shows that, for the condition of all the other remaining parameters being fixed, more gas is released in a MOX fuel for lower number density of, smaller size of, and larger fraction of Pu retained in, the Pu-rich particles. However, there exists some condition or combination of parameters for which the effect of inhomogeneity on gas release is negligible depending on the characteristics of MOX fuel. Comparison with measured data for OCOM MOX fuel shows that the present model can predict the level of gas release in MOX fuel once the release mechanism in the Pu-rich particles is known.     

Behavior of Si impurity in Np-Am-MOX fuel irradiated in the experimental fast reactor Joyo

The irradiation behavior of uranium-plutonium mixed oxide fuels containing a large amount of silicon impurity was examined by post-irradiation examination. Influences of Si impurity on fuel restructuring and cladding attack were investigated in detail. Si impurity, along with Am, Pu and O were transported by spherical pores and cylindrical tubular pores to the fuel center during fuel restructuring of the Np-Am-MOX fuel, where a eutectic reaction of fuel and Si-rich inclusions occurred. After fuel restructuring of the Np-Am-MOX fuel, Si-rich inclusions without fuel constituents were agglomerated at fuel crack openings where shallow attacks on the inner wall of the cladding were seen. Such shallow attacks on the inner wall of the cladding were likewise observed near the location of fuel cracks in long-term steady-state irradiated MOX fuels. Evidence of these shallow attacks on the inner wall of the cladding remained after fuel restructuring in normal MOX fuel. However, grain boundary corrosion of the cladding inner wall at the opening of the fuel cracks was selective and was marked in MOX fuel at higher oxygen potential by the release of reactive fission products such as Cs and Te in comparison with other regions of cladding wall.     

Effects of interaction between molten zircaloy and irradiated MOX fuel on the fission product release behavior

As a first step for obtaining experimental data on the effects of high-temperature chemical interaction on fission product release behavior, we focused on the dissolution of irradiated uranium plutonium mixed oxide (MOX) fuel by molten zircaloy (Zry) and carried out a heating test under the reducing atmosphere. Pieces of an irradiated MOX fuel pellet and cladding were subjected to the heating test at 2373 K for five minutes. The fractional release rate of cesium (specifically ¹³⁷Cs) was monitored during the test and its release behavior was evaluated. The observation of microstructures and measurements of elemental distribution in the heated specimen were also performed. We demonstrated experimentally that the fuel dissolution by molten Zry accelerated the release of Cs from the fuel pellets.     

Comparative study of actinide and fission product inventory of HEU and potential LEU fuels for MNSRs

A comparative study of fuel burnup and buildup of actinides and fission products for potential LEU fuels (UO₂ and U–9Mo) with existing HEU fuel (UAl₄–Al, 90% enriched) for a typical Miniature Neutron Source Reactor (MNSR) has been carried-out using the WIMSD4 computer program. For the complete burnup, the UAl₄–Al, UO₂ and U–9Mo based systems show a total consumption of 6.89, 6.83 and 6.88 g of ²³⁵U, respectively. Relative to 0.042 g ²³⁹Pu produced in case of UAl₄–Al HEU core, UO₂ and U–9Mo based cores have been found to yield 0.793 and 0.799 g, respectively, indicating much larger values of conversion ratios and correspondingly high values of fuel utilization factor. The end-of-cycle activity of the HEU core has been found 2284 Ci which agrees well with value found by Khattab where as for UO₂ based and U–9Mo based LEU cores show 1.8 and 4.8% increase with values 2326 and 2394 Ci, respectively.     

Fission-product behaviour in irradiated TRISO-coated particles: Results of the HFR-EU1bis experiment and their interpretation

It is important to understand fission-product (FP) and kernel micro-structure evolution in TRISO-coated fuel particles. FP behaviour, while central to severe-accident evaluation, impacts: evolution of the kernel oxygen potential governing in turn carbon oxidation (amoeba effect and pressurization); particle pressurization through fission-gas release from the kernel; and coating mechanical resistance via reaction with some FPs (Pd, Cs, Sr). The HFR-Eu1bis experiment irradiated five HTR fuel pebbles containing TRISO-coated UO₂ particles and went beyond current HTR specifications (e.g., central temperature of 1523 K). This study presents ceramographic and EPMA examinations of irradiated urania kernels and coatings. Significant evolutions of the kernel (grain structure, porosity, metallic-inclusion size, intergranular bubbles) as a function of temperature are shown. Results concerning FP migration are presented, e.g., significant xenon, caesium and palladium release from the kernel, molybdenum and ruthenium mainly present in metallic precipitates. The observed FP and micro-structural evolutions are interpreted and explanations proposed. The effect of high flux rate and high temperature on fission-gas behaviour, grain-size evolution and kernel swelling is discussed. Furthermore, Cs, Mo and Zr behaviour is interpreted in connection with oxygen-potential. This paper shows that combining state-of-the-art post-irradiation examination and state-of-the-art modelling fundamentally improves understanding of HTR fuel behaviour.     

Oxidizing dissolution of spent MOX47 fuel subjected to water radiolysis: Solution chemistry and surface characterization by Raman spectroscopy

The mechanisms of oxidizing dissolution of spent MOX fuel (MIMAS TU2®) subjected to water radiolysis were investigated experimentally by leaching spent MOX47 fuel samples in pure water at 25 °C under different oxidizing conditions (with and without external gamma irradiation); the leached surfaces were characterized by Raman spectroscopy. The highly oxidizing conditions resulting from external gamma irradiation significantly increased the concentration of plutonium (Pu(V)) and uranium (U(VI)) compared with a benchmark experiment (without external irradiation). The oxidation behavior of the plutonium-enriched aggregates differed significantly from that of the UO₂ matrix after several months of leaching in water under gamma irradiation. The plutonium in the aggregates appears to limit fuel oxidation. The only secondary phases formed and identified to date by Raman spectroscopy are uranium peroxides that generally precipitate on the surface of the UO₂ grains. Concerning the behavior of plutonium, solution analysis results appear to be compatible with a conventional explanation based on an equilibrium with a Pu(OH)_4(am) phase. The fission product release - considered as a general indicator of matrix alteration - from MOX47 fuel also increases under external gamma irradiation and a change in the leaching mode is observed. Diffusive leaching was clearly identified, coinciding with the rapid onset of steady-state actinide concentrations in the bulk solution.