The steam oxidation of Cr-doped UN fuel pellets is analysed during sequential isothermal holds up to 720 degrees C. In situ neutron diffraction results show how Cr is accommodated in a secondary U2CrN3 phase, leading to the formation of a duplex UN/U2CrN3 microstructure. Under corrosion, the oxidation of the two phases begins at 400 degrees C for UN and 430 degrees C for U2CrN3, respectively. Because the UN phase is preferentially oxidised in the presence of U2CrN3, addition of Cr in UN based nuclear fuel is found to accelerate the corrosion rate. At 430 degrees C the oxidation of UN in the UN/U2CrN3 microstructure is similar to 5 times faster than pure UN, increasing to similar to 19 times faster at 460 degrees C. The oxidation of U2CrN3 produces UO2 via the formation of two transient intermediate phases. In situ neutron diffraction enables oxidation processes of UN and U2CrN3 components to be followed separately within the two-phase system.

U(X)N-based SIMFUEL samples, where X represents Zr, Nb, Mo, and Ru, were fabricated using spark plasma sintering. These samples were characterized by neutron diffraction and scanning electron microscopy to gain insights into fission product solubility and speciation at high burnup levels. The fabricated samples included pseudo-binary and higher-order compositions, allowing for the decomposition of individual fission product effects. The characterization revealed the presence of U1-xZrxN, Zr1-xUxN, ZrN, Nb1-xUx, UxNb1-x, Nb2N, URu3, Mo, and (U,Mo)Ru3 as distinct fission-product-containing phases. Notably, only Zr was found to be soluble within the primary UN fuel matrix. Significant agglomeration and formation of a (Nb-rich core)–(Nb-poor shell) microstructure was observed for the Nb-containing samples. Mo was the only fission product to form metallic inclusions and the presence of Ru led to the formation of URu3 in the pseudo-binary system (UN-10at.%Ru), or (U,Mo)Ru3 in the higher-order samples containing 1, 1.5, and 2 at.% each of all of fission product elements i.e. UN-1at.%(ZrN, Nb, Mo, Ru). No complex nitride precipitates were found to form. The phases identified in the pseudo-binary compositions were analyzed using the Thermodynamics of Advanced Fuels-International Database (TAF-ID) and showed good agreement to experimental data, except for a possible miscibility gap in the UN-ZrN tie line and absence of the (U,Mo)Ru3 phase.

The steam oxidation resistance of UN and UN-(20 vol%)ZrN fuel pellets is evaluated to enhance understanding of steam corrosion mechanisms in advanced nuclear fuel materials. In situ neutron diffraction shows the modified UN fuel pellets form a (U0.77,Zr0.23)N solid-solution and the sole crystalline oxidation product detected in bulk is (U0.77,Zr0.23)O2. U2N3 is not detected in significant quantities during the steam oxidation of UN or (U0.77,Zr0.23)N and stable lattice parameters show that hydriding does not take place. Steam oxidation rates, obtained via sequential Rietveld refinement show how (U0.77,Zr0.23)N has a higher activation energy (79 ± 1 kJmol−1 vs. 50 ± 5 kJmol−1), higher onset temperature (430 °C vs. 400 °C) and slower reaction rates for steam oxidation up to 616 °C, than pure UN. Throughout, both UN and (U0.77,Zr0.23)N exhibit linear (non-protective) oxidation kinetics, signifying that degradation of the fuel pellets is caused by the evolution of gaseous products at the interface followed by oxide scale spallation. This quantitative and mechanistic understanding of material degradation enables better defined operating regimes and points towards (U,Zr)N solid solutions as a promising strategy for the design of advanced nuclear fuel materials with enhanced steam corrosion resistance.

In this study, neutron diffraction and transmission electron microscopy (TEM) have been implemented to study the crystallographic structure of the ternary phase U2CrN3 from pellet to nano scale respectively. Recently microstructural evaluation of this ternary phase has been performed for the first time in pellet condition, overcoming the Cr evaporation issue during the conventional sintering process. In this work for the first time, the crystallographic structure of the ordered ternary U2CrN3 phase, stabilized in pellet condition, has been obtained by implementing neutron diffraction. For this study, pellets of the composite material UN with 20 vol% CrN were fabricated by powder metallurgy by mixing UN and CrN powders followed by Spark Plasma Sintering (SPS). TEM was used to investigate the nanoscale structure with a thin lamella of the order of 100–140 nm produced by focused ion beam (FIB). The neutron data revealed the phase composition of the pellet to be primarily 54(8) wt.% U2CrN3, in good agreement with the stoichiometry of starting reagents (UN and CrN powder) and metallographic analysis. Neutron data analysis confirms that all the crystallographic sites in U2CrN3 phase are fully occupied reinforcing the fully stoichiometric composition of this phase, however, the position of the N at the 4i site was found to be closer to the Cr than previously thought. TEM and selected area electron diffraction rendered nano-level information and revealed the presence of nano domains along grain boundaries of UN and U2CrN3, indicating a formation mechanism of the ternary phase, where the phase likely nucleates as nano domains in UN grains from migration of Cr.

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.

In situ neutron powder diffraction experiments are applied to physical, kinetic, and microstructural characterization of uranium mononitride as a promising light water reactor fuel material. The temperaturevariable coefficient of thermal expansion and isotropic Debye Waller factors are obtained by sequential Rietveld refinement over 499-1873 K. Oxidation of a UN pellet (95.2% density) under flow of 11 mg/min D 2 O is observed to initiate above 623 K and the rate increases by a factor of approximately 10 from 673 to 773 K, with activation energy 50.6 +/- 1.3 kJ/mol; uranium oxide is the only solid corrosion product.Crown Copyright

Thermophysical properties and oxidation behaviour of the composite pellet UN–20 vol%ZrN were investigated experimentally and compared with the behaviour of the pure UN pellet. A compound of a single phase, a solid solution of the average composition U0.8Zr0.2N, was obtained by Spark Plasma Sintering (SPS) of the powders UN and ZrN. Crystallographic and microstructural characterisation of the composite was performed using Scanning Electron Microscopy (SEM), standardised Energy Dispersive Spectroscopy (EDS) and Electron Backscatter Diffraction (EBSD). Nano hardness and Young's modulus were also measured by the nanoindentation method. High-Temperature X-ray diffraction (XRD) was applied to obtain the lattice expansion as a function of temperature (room temperature to 673 K). Thermogravimetric Analysis (TGA) was applied to evaluate oxidation behaviour in air. Results demonstrate that the fabrication method results in a matrix of solid solution with homogeneous composition averaged to U0.8Zr0.2N. The mechanical properties of such solution are uniform, with variation only due to the crystallographic orientation of the grains of the solution phase, similar to pure UN. The obtained value for the average linear thermal expansion coefficient is α¯ = 7.94 × 10-6/K, which compares well to UN (α¯ = 7.95 × 10-6/K) for the same temperature range. The degradation behaviour of the composite pellet UN-20 vol%ZrN in air shows a lower oxidation onset temperature, compared to pure UN, with the final product of oxidation being mainly U3O8. Smaller crystallites in the product of corrosion of the composite pellet indicate that the mechanism of degradation of the solid solution phase U0.8Zr0.2N is accompanied by the formation of two distinct oxides and their interaction.

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.