Gas releases and rod internal pressure of BN-added UO2 fuel

Gadolinium (Gd), in the form of gadolinia (Gd₂O₃), has been used as integral burnable absorber to UO₂ fuel by different companies. Recently, alternative burnable absorber materials are under investigation. In this paper, the results of the study on the use of boron mixed in UO₂ as an integral burnable absorber are presented. Boron nitride was selected as the form of B to be added to UO₂ fuel based on the stability of B during sintering. Fuel performance analysis code FRAPCON-UNI, which is based on FRAPCON code and has the modifications for boron and helium generation and gasses release models, was used for the calculation of fuel performance. Helium generation was calculated using a model and the result was verified against ORIGEN calculation results. Gas release calculation was based on Forsberg Massih model and different characteristics of the gasses were considered. Power histories of maximum burnup rods (B rod, no B rod, and Gd rod) were selected from reactor physics data. The results indicated significant increases in rod internal pressure by 500 ppm boron addition at the end of life with minimum influence of a grain boundary boron fraction due to high diffusivity of helium and nitrogen.     

Phase studies in the UO2-Gd2O3 system

The incorporation of gadolinium directly into nuclear fuel is important regarding reactivity compensation, which enables longer fuel cycles. The incorporation of Gd₂O₃ powder directly into the UO₂ powder by dry mechanical blending is the most attractive process, because of its simplicity. Nevertheless, processing by this method leads to difficulties while obtaining sintered pellets with the minimum required density. This is due to the bad sintering behavior of the UO₂-Gd₂O₃ mixed fuel, which shows a blockage in the sintering process that hinder the densification process. Minimal information exists regarding the possible mechanisms for this blockage and this is restricted to the hypothesis based on the formation of a low diffusivity Gd rich (U,Gd)O₂ phase. The objective of this investigation was to study the phase formation in this system, thus contributing to clarifying the causes of the blockage. Experimental evidence indicated the existence of phases in the (U,Gd)O₂ system that revealed structures different from the fluorite-type UO₂ structure. These phases appear to be isostructural to the phases observed in the rare earth-oxygen system.     

Thermal conductivities of irradiated UO2 and (U, Gd)O2 pellets

Thermal diffusivities of UO₂ and (U, Gd)O₂ pellets irradiated in a commercial reactor (maximum burnups: 60 GWd/t for UO₂ and 50 GWd/t for (U, Gd)O₂) were measured up to about 2000 K by using a laser flash method. The thermal diffusivities of irradiated UO₂ and (U, Gd)O₂ pellets showed hysteresis phenomena: the thermal diffusivities of irradiated pellets began to recover above 750 K and almost completely recovered after annealing above 1400 K. The thermal diffusivities after recovery were close to those of simulated soluble fission products (FPs)-doped UO₂ and (U, Gd)O₂ pellets, which corresponded with the recovery behaviors of irradiation defects for UO₂ and (U, Gd)O₂ pellets. The thermal conductivities for irradiated UO₂ and (U, Gd)O₂ pellets were evaluated from measured thermal diffusivities, specific heat capacities of unirradiated UO₂ pellets and measured sample densities. The difference in relative thermal conductivities between irradiated UO₂ and (U, Gd)O₂ pellets tended to become insignificant with increasing burnups of samples.     

Application of genetic algorithms to optimize burnable poison placement in pressurized water reactors

An efficient and a practical genetic algorithm (GA) tool was developed and applied successfully to Burnable Poison (BP) placement optimization problem in the reference Three Mile Island-1 (TMI-1) core. Core BP optimization problem means developing a BP loading map for a given core loading pattern that minimizes the total Gadolinium (Gd) amount in the core without violating any design constraints. The number of UO₂/Gd₂O₃ pins and Gd₂O₃ concentrations for each fresh fuel location in the core are the decision variables. The objective function was to minimize the total amount of Gd in the core together with the residual Gd reactivity binding at the End-of-Cycle (EOC). The constraints are to keep the maximum peak pin power during the core depletion and soluble boron (SOB) concentration at the Beginning of Cycle (BOC) both less than their limit values. The innovation of this study was to search all of the possible UO₂/Gd₂O₃ fuel assembly designs with variable number of UO₂/Gd₂O₃ fuel pins and concentration of Gd₂O₃ in the overall decision space. The use of different fitness functions guided the solution towards desired (good solutions) region in the solution space, which accelerated the GA solution. The main objective of this study was to develop a practical and efficient GA tool and to apply this tool to designing an optimum BP pattern for a given core loading.     

Activation Analysis of Gadolinium Impurity in High Purity Europium Oxide

Abstract

An analytical method for determining Gd impurity in high purity Eu₂O₃ is proposed, which makes use of neutron activation and cation-exchange separation to examine its suitability as target material for the production of ^{152 m, 152, 154}Eu.

Long-term irradiation of an Eu sample resulted in ¹⁵³Gd activity amounting to 1.8 times that of the same nuclide produced from an equal quantity of Gd by (n, γ) reaction. This experimental value is quite consistent with that obtained by calculation under the assumption that the ¹⁶³Gd results from nuclear reaction on ¹⁵¹Eu induced by secondary neutrons.

For the accurate determination of Gd, Gd impurity was separated from the Eu sample prior to neutron irradiation in order to reduce the self-shielding effect in the Eu sample. Separation by cation-exchange with α-hydroxyisobutyrate (0.33 M, pH 3.77) made it possible to reduce the content of Eu in the Gd fraction below 7×10^?3%. This sufficed to assure that the ¹⁵⁹Gd content in ^152mEu was smaller than 1×10^?3%. For the determination of Gd content below 10⁴ ppm, however, should necessitate further purification of the irradiated Gd fraction.     

A mechanism for the sintered density decrease of UO2–Gd2O3 pellets under an oxidizing atmosphere

A mixture of UO₂ and Gd₂O₃ powders was pressed into compacts and sintered under various atmospheres ranging from reducing to oxidizing gases. The sintered density of UO₂–10 wt% Gd₂O₃ pellets decreases with increasing oxygen potential of the sintering atmosphere. Dilatometry and X-ray diffraction studies indicate that the delay of densification takes place between 1300°C and 1500°C, along with the formation of (U,Gd) O₂. A very large solubility of Gd₂O₃ in UO₂ relative to the reverse solubility might cause Gd ions to diffuse into UO₂ so directionally that new pores are produced at the places of Gd₂O₃ particles. The new pores may be difficult to shrink and thus lead to the density decrease under an oxidizing atmosphere but not under a reducing atmosphere, because a driving force for the shrinkage of new pores may be smaller under an oxidizing atmosphere than under a reducing atmosphere.     

Optimized gadolinia concepts for advanced in-core fuel management in PWRs

Utilities operating LWRs require fuel assemblies and in-core fuel management service, which ensure safe, flexible and cost-effective production of electricity. Because the reliability of the fuel has always been the most important requirement, advanced measures to minimize fuel cycle costs are receiving increasing attention in the light of the pressure on costs within the deregulated power generation markets. The role of in-core fuel management in supporting the goal to minimize fuel cycle costs consists in the development of more demanding core loading strategies, i.e. in the first place, more advanced low leakage loading patterns. A prerequisite for this type of loading pattern is the use of an optimized burnable absorber design. Gadolinia (Gd) as integrated burnable absorber is a very effective means for limiting the critical boron concentration and power peaking factors. Current development efforts for optimizing Gd-fuel are focused on the reduction of the inherent penalties of today's Gd-FA designs, i.e. reduced average fuel assembly (FA) enrichment and heavy metal content, as well as the residual reactivity binding. The most effective way to overcome these drawbacks is the reduction of the Gd₂O₃ concentration to values of ≈2 w/o, for which, according to recent measurements of the heat conductivity of modern Gd-fuels, the reduction of the fissile content in the Gd-rods is no longer necessary. Various feasibility studies have been performed to evaluate the consequences of FA designs with low Gd-concentrations (low-Gd designs) for Siemens PWRs and non-Siemens PWRs, for which more restrictive boundary conditions with respect to critical boron concentration and peaking factors have to be fulfilled. These studies, as well as operation experience of reactor cycles using low Gd-FA reload designs, confirm that the in-core fuel management can handle the different Gd burnout characteristics without problems. The economical benefits of low-Gd designs compared to conventional Gd designs are comparable to those achievable by distinctly more costly and complex alternatives, like the use of enriched gadolinia.     

Compatibility of Eu2O3 and (Eu,Gd)2O3 with Type 316 Stainless Steel

The compatibility of Eu₃O₃ and (Eu,Gd) ₂O₃ mixed oxides which contain 0, 1, 5, 10, 50 and 100 mol% of Gd₂O₃, with type 316 stainless steel was examined by out-of-pile heatings. The heating temperature ranged from 550 to 1,000°C and heating time from 500 h to up to 5,000 h. Metallographic examinations of the stainless steel indicated that chemical reaction between Eu₂O₃ and stainless steel occurred at 650°C and that grain boundary penetration extended up to 40 μ m after heating at 1,000°C for 500 h. The penetration depth Δ was expressed as a function of heating temperature T as

Δ = 3.08 × 10⁴ exp(?1.72 × 10²RT)

where R is the gas constant and the activation energy is given in cal/mol. Electron probe microanalysis and X-ray diffraction analysis indicated that main reaction product is europium silicate. When Gd, which is a decay product of Eu, is mixed with Eu₂O₃, the degree of reaction between (Eu,Gd) ₂O₃ and stainless steel decreases as increase in concentration of Gd₂O₃. It was found that actually no grain boundary attack was observed even after heating at 1,000°C for 500 h when concentration of Gd₂O₃;i in (Eu,Gd) ₂O₃ exceeded 10 Discussion was made of reaction mechanism of Eu₂O₃ and (Eu,Gd) ₂O₃ with stainless steel.     

Defect engineering in the MOSLED structure by ion implantation

When amorphous SiO₂ films are bombarded with energetic ions, various types of defects are created as a consequence of ion-solid interaction (peroxy radicals POR, oxygen deficient centres (ODC), non-bridging oxygen hole centres (NBOHC), E′ centres, etc.). The intensity of the electroluminescence (EL) from oxygen deficiency centres at 2.7 eV, non-bridging oxygen hole centres at 1.9 eV and defect centres with emission at 2.07 eV can be easily modified by the ion implantation of the different elements (H, N, O) into the completely processed MOSLED structure. Nitrogen implanted into the SiO₂:Gd layer reduces the concentration of the ODC and NBOHC while the doping of the oxygen increases the EL intensity observed from POR defect and NBOHC. Moreover, after oxygen or hydrogen implantation into the SiO₂:Ge structure fourfold or fifth fold increase of the germanium related EL intensity was observed.     

Mössbauer study and structural characterization of UO2–Gd2O3 sintered compounds

Samples of UO₂and up to 10 wt% of Gd₂O₃ were prepared by solid-state reaction under a reducing atmosphere, in a thermal path comprising ramps and dwell times in the temperature range of 900–1750 °C. The sintered material was analyzed by X-ray diffraction and ¹⁵⁵Gd Mössbauer spectroscopy. The results showed that for samples annealed up to 900 °C, the gadolinium sesquioxide remained unreacted. However, when the temperature was increased to 1300 °C, a solid-state reaction took place forming mixed oxides. For the more severe sintering condition, at 1750 °C, gadolinia left urania partially unreacted producing a material consisting of two compositions, UO₂ (with no dissolved gadolinium) and (U, Gd)O₂. The proposed heating cycle provided pellets free from Gd₂O₃ phase and may be used by the nuclear fuel industry as a suitable sintering process.     

Electronic sputtering of Gd3Ga5O12 and Y3Fe5O12 garnets: Yield, stoichiometry and comparison to track formation

The results of present paper have shown that sputtering of yttrium iron garnet (Y₃Fe₅O₁₂) under swift heavy ions in the electronic energy loss regime is non-stoichiometric. Here we are presenting additional experimental results for gadolinium gallium garnet (Gd₃Ga₅O₁₂) as target. The irradiations were performed with different ions (⁵⁰Cr (589 MeV), ⁸⁶Kr (195 MeV) and ¹⁸¹Ta (400 MeV)) impinging perpendicularly to the surface. As earlier, the sputtering yield was determined by collecting the emitted gadolinium and gallium atoms on a thin aluminium foil, placed upstream above the target and analyzing the Al catcher by Rutherford backscattering. Also for Gd₃Ga₅O_12, the emission of Gd and Ga is non-stoichiometric. Sputtering appears above a critical electronic stopping power of S_th = 11.6 ± 1.5 keV/nm, which is larger than the threshold for track formation, in agreement with other amorphisable materials. In addition, the angular distribution of the sputtered species was measured for Y₃Fe₅O₁₂ and Gd₃Ga₅O₁₂ using 200 MeV Au ions impinging the surface at 20° relatively to the surface. For the two garnets the ratio of Y/Fe (and Gd/Ga) varies with the angle of emitted species and the stoichiometry seems to be preserved only for an emission perpendicular to the surface.     

Comparison of Calculated Values with Measured Values on the Amount of TRU and FP Nuclides Accumulated in Gadolinium Bearing PWR Spent Fuels

Destructive analyses for five spent fuel samples taken from a Gd bearing fuel assembly were done. The measured amounts of actinides of ^234-238U, ²³⁷Np, ^238-242p_u 241,242m,243Am ^242,244Cm, and fission products of ¹³⁴Cs and ¹⁵⁴Eu were used for evaluating the accuracy of calculation made by CASMO-MICBURN and ORIGEN-2 codes. The effect of Gd on the neutron spectrum was taken into account in the CASMO-MICBURN calculation.

The amounts of ²³⁵U, ²³⁹Pu and ²⁴¹Pu calculated by CASMO-MICBURN agreed well with the observed values within about 3%. On the other hand, the amounts obtained from ORIGEN-2 calculation showed lower values than those observed, especially by —12% in average in ²³⁵U for Gd₂0₃U0₂ fuel. The main cause of this large difference may be attributed to the effect of Gd on the neutron spectrum. The amounts of the other actinides by both calculation codes revealed no significant difference in nearly 10% except for ^242mAm, in which a large fluctuation among the samples was observed. About 10% difference between the measured values and the calculated values was also observed for ¹³⁴Cs, but the calculated values for ¹⁵⁴Eu showed a significant difference from measured values.     

Remarks on the sintering behavior of UO2-Gd2O3 fuel

The previous work by our group showed experimental evidence that supports the idea that a diffusion barrier is formed around Gd₂O₃ agglomerates due to the formation of gadolinium-rich (U,Gd)O₂ phases with low diffusivity. This would be the reason for the bad sintering behavior of the UO₂-Gd₂O₃ fuel. The objective of this investigation was to confirm that hypothesis by direct experimental evidence. Analysis of the results showed that the diffusion barrier hypothesis is not applicable.     

A benchmarked MCNP model of the in vivo detection of gadolinium by prompt gamma neutron activation analysis

Gadolinium (Gd)-based contrast agents are a valuable diagnostic aid for magnetic resonance imaging (MRI). The amount of free Gd deposited in tissues following contrast enhanced MRI is of toxicological concern. The McMaster University in vivo prompt gamma neutron activation analysis facility has been adapted for the detection of Gd in the kidney, liver, and the leg muscle. A simple model of the HPGe detector used for detection of the prompt γ-rays following Gd neutron capture has been created using Monte Carlo simulation. A separate simulation describing the neutron collimation and shielding apparatus has been modified to determine the neutron capture rate in the Gd phantoms. The MCNP simulation results have been confirmed by experimental measurement. The deviations between MCNP and the experiment were between 1% and 18%, with an average deviation of 3.8 ± 6.7%. The validated MCNP model is to be used to improve the Gd in vivo measurement sensitivity by determining the best neutron moderator/reflector arrangement.     

Gadolinium Isotope Separation by Cation Exchange Chromatography

Displacement chromatographies of Gd adsorption band in cation exchange resin were performed to observe the isotope effects in the Gd ion exchange processes involving complex forming reagents. The heavy isotope of ¹⁶⁰Gd was found to be enriched at the front boundary of Gd adsorption band and the lighter isotopes of 1MGd, ¹⁵⁶Gd and ¹⁵⁷Gd were enriched at the rear boundary in both cases of 20.1m elution with EDTA and 14 m elution with malic acid, as predicted in the theoretical relations. Observed separation coefficients are 4.9×10^?5, 4.0×10^?5 and 2.5×10^?5for isotopie pairs of ^{156 160}Gd, ¹⁵⁸Gd and ¹⁶⁰Gd, respectively, in the case of EDTA elution. In the case of malic acid elution, smaller separation coefficients were observed as 1.8×10^?5, 1.6 ⁵O^?5 and 0.92×10^?5 for isotopie pairs of ^{156 160}Gd, ¹⁵⁷Gd and^{158 160} respectively.     

Electrochemical behaviour of gadolinium ion in molten LiCl-KCl eutectic

This work presents the electrochemical study of GdCl₃ in the molten LiCl-KCl eutectic in the temperature range 723-823 K. Transient electrochemical techniques such as cyclic voltammetry and chronopotentiometry, on an inert metallic tungsten working electrode, have been used in order to investigate the reduction mechanism and transport parameters. This study shows that Gd³⁺ ions are reduced to Gd metal by a single step mechanism with exchange of three electrons. Diffusion coefficient of GdCl₃ ions was determined at various temperatures, at 723 K the value is D = 0.88 10⁻⁵ cm² s⁻¹. Apparent standard reduction potential of the redox couple Gd³⁺/Gd has been determined by the open-circuit chronopotentiometry technique at several temperatures. Also the Gibbs free energy of GdCl₃ formation was determined and compared with thermodynamic data for pure compounds in the supercooled state in order to estimate the activity coefficient of Gd³⁺ in the molten LiCl-KCl eutectic.     

Development and evaluation of a new Eu/SmPd3 source for use with Gd Mössbauer spectroscopy

A ¹⁵⁵Eu/¹⁵⁴SmPd₃ (about 231 MBq) source for use with ¹⁵⁵Gd Mössbauer spectroscopy was developed by a novel method. In the novel method, the isotopically enriched ¹⁵⁴SmPd₃ compound was prepared by the conventional solid state reaction of ¹⁵⁴Sm(HCOO)₃ and PdH_x in a hydrogen atmosphere at 1273 K for 18 h, which is simpler than the previously reported method. In order to increase the reaction areas, palladium fine particles used to synthesize the PdH_x hydride were prepared by a chemical solution process. Performance of the newly developed source was evaluated by observing the ¹⁵⁵Gd Mössbauer spectra of known compounds, GdPd₃ and cubic Gd₂O₃ at 12 K. The obtained results indicated that the developed source is fine enough to investigate the structural characteristic of various materials containing gadolinium.     

Thermal conductivity of rare earth-uranium ternary oxides of the type RE6UO12

The knowledge of thermophysical properties of the rare earth uranium ternary oxides of the type RE₆UO₁₂ (RE=La, Gd and Dy) is essential to understand the fuel performance during reactor operation and for modeling fuel behavior. Literature on the high temperature properties of this compound is not available and there is no report at all on the thermal conductivity of these compounds. Hence a study of thermal conductivity of this compound has been taken up. The compounds were synthesized by a solution combustion method using metal nitrates and urea. Thermal diffusivity of these compounds was measured by the laser flash method in the temperature range 673-1373 K. The specific heat data was computed using Neumann-Kopp’s law. Thermal conductivity was calculated using the measured thermal diffusivity value, density and specific heat data for different temperatures. The temperature dependence of thermal conductivity and the implication of structural aspects of these compounds on the data are discussed here.     

DHDECMP-TBP/煤油从模拟高放废液中萃取回收Am-Gd的研究

研究了ＤＨＤＥＣＭＰ－ＴＢＰ／煤油萃取Ａｍ＾３＋、Ｇｄ＾３＋的各影响因素,在单级萃取实验的基础上,用０．６０ｍｏｌ／ＬＤＨＤＥＣＭＰ－１．４０ｍｏｌ／ＬＴＢＰ／煤油为有机相对模拟高放废液进行了逆流串级萃取实验降流串级反萃实验,成功地从模拟高放废液中分离回收了Ａｍ＾３＋和Ｇｄ＾３＋。     

Glass-ceramic nuclear waste forms obtained from SiO2-Al2O3-CaO-ZrO2-TiO2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): study of internal crystallization

Glass-ceramic waste forms such as zirconolite (nominally CaZrTi₂O₇) based ones can be envisaged as good candidates for minor actinides or Pu immobilization. Such materials, in which the actinides (or lanthanides used as actinide surrogates) would be preferentially incorporated into zirconolite crystals homogeneously dispersed in a durable glassy matrix, can be prepared by controlled crystallization (nucleation + crystal growth) of parent glasses belonging to the SiO₂-Al₂O₃-CaO-ZrO₂-TiO₂ system. In this work we present the effects of the nature of the minor actinide surrogate (Ce, Nd, Eu, Gd, Yb, Th) on the structure, the microstructure and the composition of the zirconolite crystals formed in the bulk of the glass-ceramics. The amount of lanthanides and thorium incorporated into zirconolite crystals is discussed in relation with the capacity of the glass to accommodate these elements and of the crystals to incorporate them in the calcium and zirconium sites of their structure.