Uranium nitride (UN)-uranium dioxide (UO2) composite fuels are being considered as an accident tolerant fuel (ATF) option for light water reactors. However, the complexity related to the chemical interactions between UN and UO(2 )during sintering is still an open problem. Moreover, there is a lack of knowledge regarding the influence of the sintering parameters on the amount and morphology of the alpha-U2N3 phase formed. In this study, a detailed investigation of the interaction between UN and UO2 is provided and a formation mechanism for the resulting alpha-U2N3 phase is proposed. Coupled with these analyses, an innovative ATF concept was investigated: UN microspheres and UO2,13 powder were mixed and subsequently sintered by spark plasma sintering. Different temperatures, pressures, times and cooling rates were evaluated. The pellets were characterised by complementary techniques, including XRD, DSC, and SEM-EDS/WDS/EBSD. The UN and UO2 interaction is driven by O diffusion into the UN phase and N diffusion in the opposite direction, forming a long-range solid solution in the UO2 matrix, that can be described as UO2-xNx. The cooling process decreases the N solubility in UO2-xNx, causing then N redistribution and precipitation as alpha-U2N3 phase along and inside the UO2 grains. This precipitation mechanism occurs at temperatures between 1273 K and 973 K on cooling, following specific crystallographic grain orientation patterns.

Uranium nitride (UN)-uranium dioxide (UO2) composites have been proposed as an innovative advanced technology fuel (ATF) option for light water reactors (LWRs). However, the interdiffusion of oxygen and nitrogen during fabrication result in the formation of α-U2N3. A way to avoid this interaction is to coat the UN with a material that is impermeable to oxygen and nitrogen, has a high melting point, high thermal conductivity, and reasonable low neutron cross-section. Among many candidates,refractory metals may be the first option. In this study, we present an early progressresult of fabricating an innovative ATF concept: coated UN microspheres embedded in UO2 matrix. To do so, the following steps are performed: 1) diffusion couple experiments of UN-X-UO2 (X=W, Mo, Ta, Nb, V) to evaluate the interactions between the coating candidates (X) and the fuels; 2) selection of the most promising candidates; 3) use a surrogate material (ZrN microspheres) to develop processes to coat the microspheres with nanopowders: dry and wet methods; 4) coating the UN microspheres with a selected method; 5) finally, sinter a coated UN-UO2 composite using spark plasma sintering (SPS), and compare the results with an uncoated UNUO2 composite sintered at the same SPS conditions (1500 °C, 80 MPa, 3 min,vacuum). The diffusion couple results indicate W and Mo as the most promising candidates, with the wet method showing the smoothest surface. So, dense (~95 %TD) W/UN-UO2 and Mo/UN-UO2 were sintered and the preliminary results show that the tungsten coating was not efficient due to poor adhesion. Conversely, the Mo coating (~15 µm) was efficient against the α-U2N3 formation. Therefore, this early progress indicates the possibility of fabricating an innovative ATF concept using a low cost and potentially applicable coating method.

Uranium nitride (UN) spheres embedded in uranium dioxide (UO₂) matrix is considered an innovative accident tolerant fuel (ATF). However, the interaction between UN and UO₂ restricts the applicability of such composite in light water reactors. A possibility to limit this interaction is to separate the two materials with a diffusion barrier that has a high melting point, high thermal conductivity, and reasonably low neutron cross-section. Recent density functional theory calculations and experimental results on interface interactions in UN-X-UO₂ systems (X = V, Nb, Ta, Cr, Mo, W) concluded that Mo and W are promising coating candidates. In this work, we develop and study different methods of coating ZrN spheres, used as a surrogate material for UN spheres: first, using Mo or W nanopowders (wet and binder); and second, using chemical vapour deposition (CVD) of W. ZrN-UO₂ composites containing 15 wt% of coated ZrN spheres were consolidated by spark plasma sintering (1773 K, 80 MPa) and characterised by SEM/FIB-EDS and EBSD. The results show dense Mo and W layers without interaction with UO₂. Wet and binder Mo methods provided coating layers of about 20 µm and 65 µm, respectively, while the binder and CVD of W methods layers of about 12 µm and 3 µm, respectively.

UN-UO₂ composites are considered an accident tolerant fuel (ATF) option for light water reactors (LWRs). However, the interactions between UN and UO2 and the low oxidation resistance of UN limit the application of such ATF composite concept in LWRs. A potential alternative to overcome these issues is encapsulating the UN fuel before sintering. Based on our recent studies, molybdenum and tungsten are selected to encapsulate UN spheres. In this article, different coating techniques, such as powder coating, chemical vapour deposition (CVD), and physical vapour deposition (PVD), were developed and applied to encapsulate surrogates and UN spheres. Encapsulated UN-UO₂ pellets fabricated by the spark plasma sintering (SPS) method (1773 K, 80 MPa) were characterised by complementary techniques and evaluated against their oxidation resistance in air up to 973 K. The results show inert, dense, and non-uniform Mo and W layers of about 28 μm and 32 μm, respectively, obtained by the powder coating method. PVD provided uniform and dense layers of Mo and W of approximately 1.0 μm and 4.0 μm, respectively, but with cracks at the interface with the surrogate spheres. PVD-Mo onto UN spheres shows a dense and well-adhered layer of about 0.5 μm but with W contamination from the previous coating. The PVD-W and CVD-W results and the oxidation experiments will be in the final version of this manuscript.

Composite fuels such as UN-UO2 are being considered to address the lower oxidation resistance of the UN fuel from a safety perspective for use in light water reactors, whilst improving the in-reactor behaviour of the more ubiquitous UO2 fuel. An innovative UN-UO2 accident tolerant fuel has recently been fabricated and studied: UN microspheres embedded in UO2 matrix. In the present study, detailed oxidative thermogravimetric investigations (TGA/DSC) of high-density UN/U2N3-UO2 composite fuels (91-97 %TD), as well as post oxidised microstructures obtained by SEM, are reported and analysed. Triplicate TGA measurements of each specimen were carried out at 5 K/min up to 973 K in a synthetic air atmosphere to assess their oxidation kinetics. The mass variation due to the oxidation reactions (%), the oxidation onset temperatures (OOTs), and the maximum reaction temperatures (MRTs) are also presented and discussed. The results show that all composites have similar post oxidised microstructures with mostly intergranular cracking and spalling. The oxidation resistance of the pellet with initially 10 wt% of UN microspheres is surprisingly better than the UO2 reference. Moreover, there is no significant difference in the OOT (similar to 557 K) and MRT (similar to 615 K) when 30 wt% or 50 wt% of embedded UN microspheres are used. Therefore, the findings in this article demonstrate that the UO2 matrix acts as a barrier to improve the oxidation resistance of the nitride phases at the beginning of life conditions.

In this study, the temperature-dependent effective thermal conductivity of the innovative UN-X-UO₂ (X=Mo, W) nuclear fuel composite has been estimated in the temperature range from room temperature to 2000 K. This composite fuel concept is considered as a promising accident tolerant fuel for light water reactors (LWRs). Following the previously reported experimental composite design, the composite fuel thermal conductivity was calculated using Finite Element modeling (FEM), and it is compared with analytical models of thermal conductivity for 10, 30, 50, and 70 wt.% uncoated/coated UN microspheres in a UO₂ matrix. The FEM results show an expected increase in the fuel thermal conductivity as the wt.% of the coated/uncoated UN microspheres increases – from 1.5 to 5.7 times the UO₂ reference at 2000 K. However, the analytical models show an overestimation of the fuel thermal conductivity as the wt.% increases. The results also show that Mo and W coatings have similar thermal behaviors and the coating thickness varying from 1-5 μm has an insignificant effect on the thermal behavior of the composite. However, at higher weight fractions, the thermal conductivity of the fuel composite at room temperature is substantially influenced by the high thermal conductivity coatings exceeding that of UN. Thereafter, the thermal conductivity profiles from FEM were used in the fuel thermal performance evaluation during LWR normal operation to calculate the maximum centerline temperature of the fuel composites. The results show a significant decrease in the fuel maximum centerline temperature ranging from −72 K for 10 wt.% UN to −438 K for 70 wt.% UN compared to the UO₂ under the same irradiation conditions, providing an enhanced safety margin and thermal and neutronic advantages.