Improvement of UO2 Pellet Properties by Controlling the Powder Morphology of Recycled U3O8 Powder

Powder morphology evolution of recycled U₃O₈ according to the thermal treatments has been studied. The defective UO₂ pellets are oxidized to U₃O₈ powders at a conventional temperature of 350 or 450°C in air. Those powders are pressed into green pellets and then sintered at 1,500 and 1,730°C in H₂ gas flow. Final reoxidized U₃O₈ powers are obtained by reoxidizing those sintered pellets at 450°C in air. This paper shows that the reoxidized U₃O₈ powder morphology and the BET surface areas are greatly dependent on the density of sintered UO₂ pellets before reoxidation. Reoxidized U₃O₈ powders are added to virgin UO₂ powders to fabricate UO₂ pellets and the effect of such addition on the UO₂ pellet properties is investigated. The reoxidized U₃O₈ powders having a certain range of BET surface area significantly promote the grain growth of UO₂ pellets.     

Treatment of UO2 pellets used for preparing fuel elements of HTR-10 followed by supercritical fluid extraction

International interest in high temperature gas-cooled reactor (HTGR) has been increasing in recent years. It is important to study on reprocessing of spent nuclear fuel from HTGR for recovery of nuclear resource and reduction of nuclear waste. Treatment of UO₂ pellets used for preparing fuel elements of the 10 MW high temperature gas-cooled reactor (HTR-10) followed by supercritical fluid extraction was investigated. When UO₂ pellets were dissolved and extracted with tri-n-butyl phosphate (TBP)–HNO₃ complex in supercritical CO₂ (SC-CO₂), the extraction efficiency was less than 7% under experimental conditions. After UO₂ pellets were ground into UO₂ fine powders, the extraction efficiency of the UO₂ fine powders with TBP–HNO₃ complex in SC-CO₂ could reach 92%. After UO₂ pellets broke spontaneously into U₃O₈ powders under O₂ flow and 600 °C, the extraction efficiency of the U₃O₈ powder with TBP–HNO₃ complex in SC-CO₂ could reach more than 98%.     

A new process based agglomeration parameter to characterize ceramic powders

Uranium dioxide powders are made through aqueous chemical route involving precipitation, drying, calcination and reduction. The presence of agglomerates causes powder packing difficulties in the compaction die, and non-uniform and incomplete densification on sintering. To quantify the degree of agglomeration, several authors have proposed ‘Agglomeration Parameters’. The change in BET specific surface area of calcined U₃O₈ upon reduction to UO₂ per unit temperature difference is a simple new measure of agglomeration in uranium dioxide powders.     

Characterization of (Th,U)O2 pellets made by advanced CAP process

Coated Agglomerate Pelletization (CAP) process is being developed by Bhabha Atomic Research Centre (BARC) for the fabrication of ThO₂-UO₂ mixed oxide fuel pellets. In order to improve the microstructures with better microhomogeneity, a study was made to modify the CAP process. The advanced CAP (A-CAP) process is similar to the CAP process except that the co-precipitated powder of mixed oxide, ThO₂-30%UO₂ or ThO₂-50%UO₂, is used for coating instead of U₃O₈ powder. The choice of ThO₂-UO₂ powders as the coating material is advantageous compared to U₃O₈, since the presence of large quantities of ThO₂ in UO₂ powder gives better self-shielding effect. In this paper, ThO₂ containing 4%UO₂ (% in weight) was prepared by the A-CAP process. Property measurements including microstructure and microhomogeneity were made by optical microscopy, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), etc. It was found that the pellets sintered in air at 1400 °C showed a duplex grain structure and those sintered in Ar-8%H₂ at 1650 °C showed a very uniform grain structure with excellent microhomogeneity.     

Fabrication method for UO2 pellets with large grains or a single grain by sintering in air

The effects of a powder treatment, the sintering temperature and the sintering time on the grain growth of UO₂ pellets were investigated in air to obtain UO₂ pellets with large grains. Air could be used for sintering because an oxidation path above 1803 K does not pass through a two-phase (UO_2+x + U₃O_8−z) region. The UO₂ pellets sintered by the CO₂-air-CO₂-H₂ process consisted of a single grain or some large grains in the order of several millimeters.     

Investigation of ThO2 and (U, Th)O2

The effect of the properties of ThO₂ and (U, Th)O₂ powders, prepared with different technological regimes, on the properties of the finished items is investigated. The work includes detailed investigations of ThO₂ and (U, Th)O₂ powders (x-ray phase analysis, electron-microscope investigation) and sintered fuel pellets (determination of density, study of microstructure, thermophysical investigations). The temperature dependences of the crystal lattice parameters and the sizes of the crystallites in ThO₂ and (U, Th)O₂ powders with different UO₂:ThO₂ ratio are obtained. The temperature dependences of the thermal conductivity of sintered ThO₂ and (U, Th)O₂ pellets with different UO₂:ThO₂ ratio are studied.     

Development of Impregnated Agglomerate Pelletization (IAP) process for fabrication of (Th,U)O2 mixed oxide pellets

Impregnated Agglomerate Pelletization (IAP) technique has been developed at Advanced Fuel Fabrication Facility (AFFF), BARC, Tarapur, for manufacturing (Th,²³³U)O₂ mixed oxide fuel pellets, which are remotely fabricated in hot cell or shielded glove box facilities to reduce man-rem problem associated with ²³²U daughter radionuclides. This technique is being investigated to fabricate the fuel for Indian Advanced Heavy Water Reactor (AHWR). In the IAP process, ThO₂ is converted to free flowing spheroids by powder extrusion route in an unshielded facility which are then coated with uranyl nitrate solution in a shielded facility. The dried coated agglomerate is finally compacted and then sintered in oxidizing/reducing atmosphere to obtain high density (Th,U)O₂ pellets. In this study, fabrication of (Th,U)O₂ mixed oxide pellets containing 3–5 wt.% UO₂ was carried out by IAP process. The pellets obtained were characterized using optical microscopy, XRD and alpha autoradiography. The results obtained were compared with the results for the pellets fabricated by other routes such as Coated Agglomerate Pelletization (CAP) and Powder Oxide Pelletization (POP) route.     

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.     

Processing of uranium oxide and silicon carbide based fuel using polymer infiltration and pyrolysis

Ceramic composite pellets consisting of uranium oxide, UO₂, contained within a silicon carbide matrix, were fabricated using a novel processing technique based on polymer infiltration and pyrolysis (PIP). In this process, particles of depleted uranium oxide, in the form of U₃O₈, were dispersed in liquid allylhydridopolycarbosilane (AHPCS), and subjected to pyrolysis up to 900 °C under a continuous flow of ultra high purity argon. The pyrolysis of AHPCS, at these temperatures, produced near-stoichiometric amorphous silicon carbide (a-SiC). Multiple polymer infiltration and pyrolysis (PIP) cycles were performed to minimize open porosity and densify the silicon carbide matrix. Analytical characterization was conducted to investigate chemical interaction between U₃O₈ and SiC. It was observed that U₃O₈ reacted with AHPCS during the very first pyrolysis cycle, and was converted to UO₂. As a result, final composition of the material consisted of UO₂ particles contained in an a-SiC matrix. The physical and mechanical properties were also quantified. It is shown that this processing scheme promotes uniform distribution of uranium fuel source along with a high ceramic yield of the parent matrix.     

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.     

Characterization of ThO2-UO2 pellets made by co-precipitation process

The co-precipitation technique renders an excellent route to obtain a homogeneous mixture of ThO₂ and UO₂ powders. In this process, after the nitrate solutions of Th and U are mixed in the intended ratio, oxalic acid is added for co-precipitation. The precipitate is then dried and calcined to get a solid solution of ThO₂ and UO₂. In this study, ThO₂-30%UO₂ and ThO₂-50%UO₂ (% in weight) powders were characterized in terms of particle size, particle shape, surface area, phase content, O/M ratio etc. The pellets obtained by sintering these powders were characterized with the help of optical microscopy, scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The XRD data for ThO₂-30%UO₂ and ThO₂-50%UO₂ pellets showed the presence of a small amount of U₃O₈ phase besides fluorite phase. The grain size of ThO₂-30%UO₂ and ThO₂-50%UO₂ was found to be 5.7 and 4.5 μm, respectively.     

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.     

Formation of columnar and equiaxed grains by the reduction of U3O8 pellets to UO2+x

The reduction of U₃O₈ pellets to UO_2+x has been investigated at 1300 °C in H₂, Ar and CO₂ gas atmospheres by TGA, SEM, and X-ray diffraction. The selected U₃O₈ pellet was prepared by sintering a U₃O₈ powder compact. The TGA results show that the reduction rate is fastest in H₂ gas, and X-ray diffraction indicates that U₃O₈ reduces to UO_2+x without any intermediate phase. The reduced pellet, UO_2+x, has a special grain structure that consists of equiaxed grains at the surface, columnar grains in the middle, and equiaxed grains in the center. The equiaxed grains and columnar grains are much smaller in H₂ gas than in Ar or CO₂ gas. The reducing gases significantly influence the morphology of the grain structure. This difference can be explained in terms of a relation between oxygen potential and critical nucleus size during the reduction.     

A non destructive technique for determination of U and Pu content in MOX fuel pins for fast reactors

MOX fuel pins containing both U²³³O₂ and PuO₂ have been fabricated for making an experimental subassembly for irradiation in Fast Breeder Test reactor (FBTR) at Kalpakkam, India. This unique composition of the fuel pin is chosen to simulate the thermo-mechanical conditions of the upcoming Prototype Fast Breeder Reactor (PFBR) in the existing Fast Breeder Test Reactor. Since the fertile matrix is natural UO_2, it was difficult to monitor the percentage of U²³³O₂ through chemical methods and neutron assay methods. During the fabrication of MOX fuel pins at Advanced Fuel Fabrication Facility; Bhabha Atomic Research Centre, Tarapur, Passive Gamma Scanning (PGS) was employed as one of the characterisation tools for verifying the fuel composition. PGS was found to be effective in estimating the percentage composition of both U²³³O₂ and PuO₂ and also in ensuring the uniform distribution of the fissile material in MOX fuel pins. PGS is also found effective in monitoring the correct loading of natural UO₂ insulation pellets and MOX fuel pellets in welded MOX pins.     

Study of the properties of ammonium polyuranate precipitates and UO<Subscript>2</Subscript> powders and pellets obtained with different technologies

The results of a differential-thermal analysis are used to compare the properties of ammonia polyuranate precipitates, UO₂ powders and pellets, obtained by different methods as well as metallic uranium. It is found that the phase NH₃·3UO₃·5H₂O forms in regular precipitation of ammonium polyuranate. When using nanotechnology, the phases NH₃·2UO₃·3H₂O and 4NH₃·6UO₃·8H₂O are also present in the precipitate. UO₂ powder prepared from such precipitate has high activity, since all phase transformations in it occur at a lower temperature. Modified fuel pellets of uranium dioxide, which are obtained by means of nanotechnology or mechanical addition of ammonia-containing reagents to powder, differ from the standard powders by a lower rate and more complex mechanism of oxidation, similar to metallic uranium. Modified UO₂ fuel pellets fabricated at the Physics and Power-Engineering Institute, are now undergoing tests in the BOR-60 reactor. After tests on the irradiated new modified fuel have been completed, it will be possible to judge its reliability.     

The influence of precipitation conditions on the properties of ammonium diuranate and uranium dioxide powders

Continuous precipitation in one and two stages was investigated to determine the effect of precipi nation variables on the properties of ADU precipitates and the sinterability of subsequent UO₂ powders in pellet fabrication. The pH at which precipitation occurred was the most important parameter in determining the size of ADU agglomerates and the settling rate and filterability of the slurry. In two-stage precipitation, the ADU properties were determined by the proportion of uranium precipitated at different pH values. Washing nitrate from ADU appeared not to affect the properties of the subsequent UO₂ pswder but a significant decrease in filterability occurred when the ADU was extensively washed. When ADU was reduced to UO₂ at 600 °C the agglomerate structure of the ADU was retained. The larger the agglomerates in the UO₂ powder (lower pH of precipitation of precursor ADU) the less sinterable it was; pseudomorphs of large agglomerates were still discernible in the sintered pellets. Thus settling rate of the ADU slurry gave an early indication of the likely sinterability of the resultant UO₂ powder since both were functions of agglomerate size.     

Effect of the heat-treatment temperature of powders on oxide fuel quality

It has been determined at the State Scientific Center of the Russian Federation—Physics and Power Engineering Institute in the course of developing a technology for fabricating various fuel compositions (UO₂+MgO, UO₂+ThO₂, UO₂+Th+ThO₂, PuO₂+MgO, UO₂+Fe+MgO, PuO₂+BaO, and others) for fast-neutron and light-water reactors that structural changes in particle aggolmerates occur at the heat-treatment stage. The optimal properties of the powders are obtained at the temperature of the morphological transformations of the particles. The fuel pellets prepared from these powders possess stable density, porosity, exterior form, mechanical strength, and so on. The total specific surface area of the oxides is an indirect parameter for estimating their quality. Each fuel composition has its own optimal powder heat-temperature temperature. 7 figures, 1 table, 5 references. State Scientific Center of the Russian Federation—A. I. Leipunskii Physics and Power-Engineering Institute. Translated from Atomnaya énergiya, Vol. 86, No. 3, pp. 189–194, March, 1999.     

Characterization and densification studies on ThO2-UO2 pellets derived from ThO2 and U3O8 powders

ThO₂ containing around 2-3% ²³³UO₂ is the proposed fuel for the forthcoming Indian Advanced Heavy Water Reactor (AHWR). This fuel is prepared by powder metallurgy technique using ThO₂ and U₃O₈ powders as the starting material. The densification behaviour of the fuel was evaluated using a high temperature dilatometer in four different atmospheres Ar, Ar-8%H₂, CO₂ and air. Air was found to be the best medium for sintering among them. For Ar and Ar-8%H₂ atmospheres, the former gave a slightly higher densification. Thermogravimetric studies carried out on ThO₂-2%U₃O₈ granules in air showed a continuous decrease in weight up to 1500 °C. The effectiveness of U₃O₈ in enhancing the sintering of ThO₂ has been established.     

Preparation,characterisation and dissolution of a CeO2 analogue for UO2 nuclear fuel

The behaviour of spent nuclear fuel under geological conditions is a major issue underpinning the safety case for final disposal. This work describes the preparation and characterisation of a non-radioactive UO₂ fuel analogue, CeO₂, to be used to investigate nuclear fuel dissolution under realistic repository conditions as part of a developing EU research programme. The densification behaviour of several cerium dioxide powders, derived from cerium oxalate, were investigated to aid the selection of a suitable powder for fabrication of fuel analogues for powder dissolution tests. CeO₂ powders prepared by calcination of cerium oxalate at 800 °C and sintering at 1700 °C gave samples with similar microstructure to UO₂ fuel and SIMFUEL. The suitability of the optimised synthesis route for dissolution was tested in a dissolution experiment conducted at 90 °C in 0.01 M HNO₃.     

Release of xenon from low-dose irradiated thoria pellets

The kinetics of post-irradiation thermal release of Xe-133 from ThO₂-0.1% UO₂ pellets of different densities, ranging from 67 to 93% theoretical density have been studied. The initial burst release (?₀) and apparent diffusivity ($\text{D'}$) decrease considerably in the case of high-density pellets (above 85% TD), which showed an abnormal increase in the closed porosity and sharp decrease in the open porosity, resulting in a large decrease in surface area. Activation energies for the release of Xe-133 have been evaluated and the possible mechanisms of release are discussed. The effect of Y₂O₃ doping (0.25 mole%) on xenon release has been studied to improve the understanding of the mechanism of rare gas migration in thoria lattice. The small decrease of diffusivity (~2–4 times) in doped pellets shows the absence of migration through cation or anion vacancies. The possible mechanism of release is discussed.