Influence of O/M ratio on sintering behavior of (U0.8, Pu0.2)O2±x

The shrinkage of (U_0.8, Pu_0.2)O_2±x pellets was investigated with the help of a thermal dilatometer in isothermal and isochronal heating tests. During shrinkage measurements in isothermal heating, the oxygen-to-metal ratio of the pellets was maintained at a constant value by controlling the oxygen potential in the sintering atmosphere. The influence of the oxygen-to-metal ratio on the sintering behavior was evaluated from the measurement results. Mainly two mechanisms dominated the sintering of mixed oxide pellets. When the oxygen-to-metal ratio was close to the stoichiometric composition, pellet shrinkage progressed at low temperatures of 1200-1600 K, and the shrinkage rate of the pellets drastically changed with a small deviation from stoichiometric composition. The result showed that a diffusion process was dominated during the sintering of near-stoichiometric compositions. On the other hand, the sintering of reduced mixed oxide pellet proceeded at high temperatures of 1600-1900 K, and the shrinkage rate was very low as compared with stoichiometric mixed oxide.     

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.     

Radiotoxicity hazard of U-free PuO2+ZrO2 and PuO2+ThO2 spent fuels in LWR

The radiotoxicity hazard of U-free Rock-like oxide: ROX (PuO₂+ZrO₂) and Thorium oxide: TOX (PuO₂+ThO₂) LWR spent fuels is investigated and radiotoxicity hazard of MOX spent fuel is considered as a reference case. The long-term ingestion radiotoxicity hazard of ROX spent fuel is one third and nearly one fourth of that of TOX and MOX spent fuels, respectively. This is because the discharged Pu and long lived Np in ROX fuel is less than that of TOX and MOX fuels. In TOX fuel, discharged Pu and MA are lower than that of MOX fuel but the long-term radiotoxicity hazard of spent fuel is nearly the same as MOX spent fuel. At the cooling 10⁵ years, the radiotoxicity hazard of TOX spent fuel is approximately ten and three times higher than that of ROX and MOX spent fuels, respectively due to higher toxic contribution of ²²⁹Th in TOX spent fuel.     

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.     

Evaluation of high plutonia (44% PuO2) MOX as a fuel for fast breeder test reactor

Uranium plutonium mixed oxide (MOX) containing up to 30% plutonia is the conventional fuel for liquid metal cooled fast breeder reactor (LMFBR). Use of high plutonia (>30%) MOX fuel in LMFBR had been of interest but not pursued. Of late, it has regained importance for faster disposition of plutonium and also for making compact fast reactors. Some of the issues of high plutonia MOX fuels which are of concern are its chemical compatibility with liquid sodium coolant, dimensional stability and low thermal conductivity. Available literature information for MOX fuel is limited to a plutonium content of 30%. Thermodynamic assessment of mixed oxide fuels indicate that with increasing plutonia oxygen potential of the fuel increases and the fuel become more prone to chemical attack by liquid sodium coolant in case of a clad breach. In the present investigation, some of these issues of MOX fuel have been studied to evaluate this fuel for its use in fast reactor. Extensive work on the out-of-pile thermo-physical properties and fuel-coolant chemical compatibility under different simulated reactor conditions has been carried out. Results of these studies were compared with the available literature information on low plutonia MOX fuel and critically analyzed to predict in reactor behaviour of this fuel containing 44% PuO₂. The results of these out-of-pile studies have been very encouraging and helped in arriving at a suitable and achievable fuel specification for utilization of this fuel in fast breeder test reactor (FBTR). As a first step of test pin irradiation programme in FBTR, eight subassemblies of the MOX fuel are undergoing irradiation in FBTR.     

Online integrated visual inspection and sorting system for fast reactor fuels

Mixed oxide (MOX) fuel for prototype fast breeder reactor (PFBR) is designed to have initial burn up of 100,000 MWD/T. The major differences from thermal reactor fuel are relatively smaller dimension with central hole and higher plutonium concentration (21% and 28% of PuO₂) MOX pellets which are loaded into 2.5 m long clad tubes with depleted UO₂ blanket pellets at either end of the MOX stack. The relatively smaller dimension of fuel pellets for PFBR results in large volume at fabrication and inspection. To ensure fast and accurate inspection and sorting of as sintered pellets with less radiation exposure to personnel an integrated on line pellet inspection system for remote visual inspection and sorting of pellets based on diameter has been developed. Details of the integrated pellet inspection system developed at Advanced Fuel Fabrication Facility, Bhabha Atomic Research Centre, Tarapur along with the results of the performance trials has been described in this paper.     

Calculations of thermodynamic properties of PuO2 by the first-principles and lattice vibration

Plutonium dioxide (PuO₂) is a key compound of mixed oxide fuel (MOX fuel). To predict the thermal properties of PuO₂ at high temperature, it is important to understand the properties of MOX fuel. In this study, thermodynamic properties of PuO₂ were evaluated by coupling of first-principles and lattice dynamics calculation. Cohesive energy was estimated from first-principles calculations, and the contribution of lattice vibration to total energy was evaluated by phonon calculations. Thermodynamic properties such as volume thermal expansion, bulk modulus and specific heat of PuO₂ were investigated up to 1500 K.     

A practical fabrication method for the advanced heterogeneous fuel with magnesia containing minor actinides

Fabrication tests on advanced heterogeneous fuel with MgO were carried out for the purpose of establishing a practical fabrication method. Advanced heterogeneous fuel consists of spheres (diameter greater than 100 μm) of a minor actinide oxide and MgO inert matrix (macro-dispersed type fuel). Macro-dispersed type fuel pellets with a high density above 90% T.D. were successfully fabricated. In addition, the fabricated pellets showed a homogeneous dispersion of near spherical host phase granules. These were attained by optimization of the fabrication process and conditions; i.e. a preliminary heat treatment of raw powders of host phase, an adjustment of pressure at the granulation process, deployment of a spray-dry process for MgO sphere preparation and sintering in a He atmosphere. From these results, a practical fabrication method for MgO-based macro-dispersed type fuel based on a simple powder metallurgical technique was established.     

Mechanical properties and XRD studies of silicon carbide inert matrix fuel fabricated by a low temperature polymer precursor route

The mechanical properties of silicon carbide (SiC) inert matrix fuel (IMF) pellets fabricated by a low temperature (1050 °C) polymer precursor route were evaluated at room temperature. The Vickers hardness was mainly related to the chemical bonding strength between the amorphous SiC phase and the β-SiC particles. The biaxial fracture strength with pre-notch and fracture toughness were found to be mostly controlled by the pellet density. The maximum Vickers hardness, biaxial fracture strength with pre-notch and fracture toughness achieved were 5.6 GPa, 201 MPa and 2.9 MPa m^1/2 respectively. These values appear to be superior to the reference MOX or UO₂ fuels. Excellent thermal shock resistance for the fabricated SiC IMF was proven and the values were compared to conventional UO₂ pellets. XRD studies showed that ceria (PuO₂ surrogate) chemically reacted with the polymer precursor during sintering, forming cerium oxysilicate. Whether PuO₂ will chemically react in a similar manner remains unclear.     

UO_2-多壁碳纳米管复合燃料芯块的制备工艺

分别采用热压烧结与无压烧结工艺制备了掺杂5%~20%多壁碳纳米管(MWNTs)的UO2复合燃料芯块,分析了芯块的性能。结果表明:乙醇湿法球磨可将MWNTs均匀分散到UO2基体中;热压烧结芯块随MWNTs含量的增加,芯块密度逐渐下降,MWNTs含量为5%的芯块密度为96.7%TD;无压烧结芯块随MWNTs含量的增加,芯块密度先升高后降低,MWNTs含量为12.5%的芯块密度最高,为97.2%TD;1 400℃、50 MPa热压烧结工艺,MWNTs与UO2基体未发生反应;1 750℃无压烧结工艺,MWNTs与UO2基体产生微弱反应生成少量UC相;SEM显示,MWNTs在UO2基体以沿晶和穿晶状态分布;在250℃,热压烧结UO2-10%MWNTs芯块热导率为6.76 W/(m·K),提高了20.28%;无压烧结UO2-12.5%MWNTs芯块热导率为6.65 W/(m·K),提高了18.33%。     

A fabrication technique for a UO2 pellet consisting of UO2 grains and a continuous W channel on the grain boundary

A new fabrication process of UO₂-W composite fuel has been studied in order to improve the thermal conductivity of the UO₂ pellet by the addition of a small amount of W. A fabrication process was designed from the phase equilibria among tungsten, tungsten oxides and UO₂. The conventionally sintered UO₂ pellet which contains W particles is heat-treated in an oxidizing gas and then in a reducing gas. In the oxidizing heat-treatment W particles are oxidized and liquid tungsten oxide penetrates within the UO₂ grain boundary, and in the reducing heat-treatment liquid oxide is transformed to solid tungsten which forms a continuous channel along the UO₂ grain boundary. This developed technique can provide a continuous W channel covering UO₂ grains for a UO₂-W composite fuel even with a small amount of a metal phase - below 6 vol.%. The thermal diffusivity of the UO₂-6 vol.%W cermet composite increases by about 80% when compared with that of a pure UO₂ pellet.     

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 of Mixed Urianium–Plutonium Fuel on the Paket Setup and Waste Handling Methods

The results of fabrication of fuel elements with mixed uranium–plutonium oxide fuel are presented. The experimental fuel assemblies assembled from the fuel elements were tested in BN-350 and -600 reactors. Postreactor investigations of the fuel elements showed that there was no substantial difference in the behavior of the fuel cores consisting of the mixed fuel as compared with UO₂ fuel. Solid and liquid radioactive wastes are produced during the fuel fabrication process. A classification of the wastes and methods for handling them is given. It is shown that the off-grade sintered pellets should be pulverized and returned to the beginning of the mixed-fuel fabrication process.     

Wet granulation of mixed oxide powders de-nitrated by the microwave heating

A performance in a wet granulation of mixed oxide (MOX) powders prepared by the microwave heating de-nitration method was examined to fabricate MOX fuel pellets for fast breeder reactor at an extremely simplified process. An agitating granulator equipped with three blades and a chopper was used and its performance was evaluated. Characteristics and physical properties of the raw powder and the granules were measured together with observations by scanning electron microscopy before/after granulation. We could obtain the granules of 120–140 μm in diameter within a narrow range of water addition ratio 12.5–13.5 wt% combined with a flow-ability >73 and a product yield >90%. Specific surface area that corresponds to sintering performance was almost the same as that of raw powder. When the ratio was <9 wt%, no granule was observed, and flow-ability did not change from that of raw powder <30. It was estimated from an additional experiment that the reason was capillaries (or voids) in the raw powder. When the ratio was more than 14 wt%, the flow-ability saturated and the product yield decreased. This narrow range of water addition ratio and strong binding force were successfully understood based on the standard theory of granulation supposing the Pendular state and the Gorge method.     

An investigation on the green properties of U-10wt.%Mo/Al and U3Si2/Al powder compacts

The effects of fuel powder volume fraction and fuel particle shape on green properties of compacts, which were produced by processing the blended U-10wt.%Mo and U₃Si₂ with Al powders were investigated respectively, with respective to the compacting pressure range of 50–400 MPa. The relative density of the compacts increases with decreasing volume fraction of fuel powder. The compressibility of comminuted powder compacts was larger than that of the atomized powder compacts due to the fragmentation of comminuted particles, and the compressibility of the compacts of U-10wt.%Mo was larger than that of the compacts of U₃Si₂ due to the deformation of U-10wt.%Mo particles. The green strength of the comminuted powder compacts is higher than that of the atomized powder compact. This seems to have resulted from the smaller pore size and the larger contact area between the comminuted fuel powders and Al powders. It is suggested that the compacting condition adjustment be required to fabricate the atomized powder compacts having comparable green strength.     

Fabrication of DUPIC fuel pellets using high burn-up spent PWR fuel

Technology for the direct usage of a spent PWR fuel in CANDU reactors (DUPIC) was developed in KAERI to reduce the amount of spent fuel. DUPIC fuel pellets were fabricated using a dry processing method to re-fabricate CANDU fuel from spent PWR fuel without any intentional separation of fissile materials or fission products. The DUPIC fuel element fabrication process satisfied a quality assurance program in accordance with the Canadian standard. For the DUPIC fuels with various fuel burn-ups between 27,300 and 65,000 MWd/tU, the sintered pellet density decreased with increasing fuel burn-ups. Fission gas releases and powder properties of the spent fuel also influenced the DUPIC fuel characteristics. Measurement of cesium content released from green pellets revealed that their sintered density significantly depended on sintering temperature history. It was useful to establish a DUPIC fuel fabrication technology in which a high-burn-up fuel with 65,000 MWd/tU was treated.     

A neutronic evaluation of the (Pu–U) and (Am–Pu–U) insertion in a typical fuel of Angra-I

The goal is to evaluate the neutronic behavior when (Pu–U) and (Am–Pu–U) mixed oxide are inserted in a typical cell of a Pressurized Water Reactor (PWR) such as Angra-I. Four types of fuels were studied: (1) MOX fuel enriched at 3.1% and V_m/V_f = 1.15; (2) MOX fuel enriched at 4.5% and V_m/V_f = 1.15; (3) MOX fuel enriched at 4.5% and V_m/V_f = 2.0 and (4) MOX fuel enriched at 4.5%, with 1% of Americium insertion in its composition (62.8% of Am²⁴¹, 0.1% of Am^242m and 37.1% of Am²⁴³) and with V_m/V_f = 2.0. The first case represents the standard state of Angra I, but with Pu. The second case is similar to the first but the enrichment is increased. To evaluate the Americium insertion, a study of the V_m/V_f was made and better results were obtained with V_m/V_f = 2.0 and to compare, this case was too evaluated to (Pu–U) in the third and fourth cases. The idea is to verify the possibility of using these fuels in Angra-I analyzing neutronic parameters such as infinite multiplication factor, hardening spectrum, Boron worth and reactivity temperature coefficients. The results show that it is possible to use all the studied fuels in Angra-I as well as to burn Am inserted in the MOX fuel by a considerable quantity during PWR operation. The WIMS-D5 code was used to perform a simplified neutronic and burnup simulations to evaluate this possibility.     

Densification behaviour and sintering kinetics of ThO2-4%UO2 pellet

ThO₂-?4% ²³³UO₂ fuel will be the driver fuel for the forthcoming Advanced Heavy Water Reactor (AHWR) in India. Densification behaviour such as shrinkage and shrinkage rates of the green pellets of ThO₂-4wt.% UO₂ (natural ‘U’) fabricated by Coated Agglomerate Pelletization (CAP) process were studied using a vertical dilatometer at different heating rates. Activation energy of sintering, ‘Q’, was estimated in the initial stages of sintering by continuous rate of heating (CRH) technique as proposed by ‘Wang and Rishi Raj’ and ‘Young and Cutler’. The sintering mechanism was identified to be as the grain boundary diffusion (GBD) and the average ‘Q’ value obtained by these two methods were found to be 350 ± 16 kJ/mole and 358 ± 5 kJ/mole, respectively.     

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.