Ke Huang

U-Mo alloys are being developed as low enrichment monolithic fuel under the Reduced Enrichment for Research and Test Reactor (RERTR) program. Diffusional interactions between the U-Mo fuel alloy and Al-alloy cladding within the monolithic fuel plate construct necessitate incorporation of a barrier layer. Fundamentally, a diffusion barrier candidate must have good thermal conductivity, high melting point, minimal metallurgical interaction, and good irradiation performance. Refractory metals, Zr, Mo, and Nb are considered based on their physical properties, and the diffusion behavior must be carefully examined first with U-Mo fuel alloy. Solid-to-solid U-10 wt.%Mo versus Mo, Zr, or Nb diffusion couples were assembled and annealed at 600, 700, 800, 900 and 1000 °C for various times. The interdiffusion microstructures and chemical composition were examined via scanning electron microscopy and electron probe microanalysis, respectively. For all three systems, the growth rate of interdiffusion zone were calculated at 1000, 900 and 800 °C under the assumption of parabolic growth, and calculated for lower temperature of 700, 600 and 500 °C according to Arrhenius relationship. The growth rate was determined to be about 103 times slower for Zr, 105 times slower for Mo and 106 times slower for Nb, than the growth rates reported for the interaction between the U-Mo fuel alloy and pure Al or Al-Si cladding alloys. Zr, however was selected as the barrier metal due to a concern for thermo-mechanical behavior of UMo/Nb interface observed from diffusion couples, and for ductile-to-brittle transition of Mo near room temperature.

Metallic U-alloy fuel cladded in steel has been examined for high temperature fast reactor technology wherein the fuel cladding chemical interaction is a challenge that requires a fundamental and quantitative understanding. In order to study the fundamental diffusional interactions between U with Fe and the alloying effect of Cr and Ni, solid-to-solid diffusion couples were assembled between pure U and Fe, Fe–15 wt.%Cr or Fe–15 wt.%Cr–15 wt.%Ni alloy, and annealed at high temperature ranging from 580 to 700 °C. The microstructures and concentration profiles that developed from the diffusion anneal were examined by scanning electron microscopy, and X-ray energy dispersive spectroscopy (XEDS), respectively. Thick U6Fe and thin UFe2 phases were observed to develop with solubilities: up to 2.5 at.% Ni in U6(Fe,Ni), up to 20 at.%Cr in U(Fe, Cr)2, and up to 7 at.%Cr and 14 at.% Ni in U(Fe, Cr, Ni)2. The interdiffusion and reactions in the U vs. Fe and U vs. Fe–Cr–Ni exhibited a similar temperature dependence, while the U vs. Fe–Cr diffusion couples, without the presence of Ni, yielded greater activation energy for the growth of intermetallic phases – lower growth rate at lower temperature but higher growth rate at higher temperature.

A solid-to-solid, U-7wt.%Mo vs. Mg diffusion couple was assembled and annealed at 550°C for 96 hours. Themicrostructurein the interdiffusion zone and the development of concentration profiles were examined via scanning electron microscopy, transmission electron microscopy (TEM) and X-ray energy dispersive spectroscopy. A TEM specimen was prepared at the interface between U-7wt.%Mo andMgusing focused ion beam in-situ lift-out. The U-7wt.%Mo alloy was bonded well tothe Mg at the atomic scale, without any evidence of oxidation, cracks or pores.Despite the good bonding, very little or negligible interdiffusion was observed.This is consistent with the expectation based on negligible solubilities according to the equilibrium phase diagrams. Along with other desirableproperties, Mgis a potential inert matrix or barrier materialfor U-Mo fuel alloy systembeing developed forthe Reduced Enrichment for Research and Test Reactor (RERTR) program.

Phase constituents and microstructure changes in RERTR fuel plate assemblies as functions of temperature and duration of hot-isostatic pressing (HIP) during fabrication were examined. The HIP process was carried out as functions of temperature (520, 540, 560 and 580 °C for 90 min) and time (45–345 min at 560 °C) to bond 6061 Al-alloy to the Zr diffusion barrier that had been co-rolled with U-10 wt.% Mo (U10Mo) fuel monolith prior to the HIP process. Scanning and transmission electron microscopies were employed to examine the phase constituents, microstructure and layer thickness of interaction products from interdiffusion. At the interface between the U10Mo and Zr, following the co-rolling, the UZr2 phase was observed to develop adjacent to Zr, and the α-U phase was found between the UZr2 and U10Mo, while the Mo2Zr was found as precipitates mostly within the α-U phase. The phase constituents and thickness of the interaction layer at the U10Mo-Zr interface remained unchanged regardless of HIP processing variation. Observable growth due to HIP was only observed for the (Al,Si)3Zr phase found at the Zr/AA6061 interface, however, with a large activation energy of 457 ± 28 kJ/mole. Thus, HIP can be carried to improve the adhesion quality of fuel plate without concern for the excessive growth of the interaction layer, particularly at the U10Mo-Zr interface with the α-U, Mo2Zr, and UZr2 phases.

Metallic uranium alloy fuels cladded in stainless steel are being examined for fast reactors that operate at high temperature. In this work, solid-to-solid diffusion couples were assembled between pure U and Fe, and annealed at 853 K, 888 K and 923 K where U exists as orthorhombic α, and at 953 K and 973 K where U exists as tetragonal β. The microstructures and concentration profiles developed during annealing were examined by scanning electron microscopy and electron probe microanalysis, respectively. U6Fe and UFe2 intermetallics developed in all diffusion couples, and U6Fe was observed to grow faster than UFe2. The interdiffusion fluxes of U and Fe were calculated to determine the integrated interdiffusion coefficients in U6Fe and UFe2. The extrinsic (KI) and intrinsic growth constants (KII) of U6Fe and UFe2 were also calculated according to Wagner’s formalism. The difference between KI and KII of UFe2 indicate that its growth was impeded by the fast-growing U6Fe phase. However, the thin UFe2 played only a small role on the growth of U6Fe as its KI and KII values were determined to be similar. The allotropic transformation of uranium (orthorhombic α to tetragonal β phase) was observed to influence the growth of U6Fe directly, because the growth rate of U6Fe changed based on variation of activation energy. The change in chemical potential and crystal structure of U due to the allotropic transformation affected the interdiffusion between U and U6Fe. Faster growth of U6Fe is also examined with respect to various factors including crystal structure, phase diagram, and diffusion.

U-Mo alloys are being developed as low enrichment uranium fuels under the Reduced Enrichment for Research and Test Reactor Program. Previous investigation has shown that the interdiffusion between U and Mo in γ(bcc)-U solid solution is very slow. This investigation explored interdiffusional behavior, especially in regions with high Mo concentration, and the potential application of Mo as a barrier material to reduce the interaction between U-Mo fuel and Al alloys matrix. Solid-to-solid U-10wt.%Mo versus Mo diffusion couples were assembled and annealed at 600, 700, 800, 900 and 1000 °C for 960, 720, 480, 240, 96 h, respectively. The interdiffusion microstructures and concentration profiles were examined via scanning electron microscopy and electron probe microanalysis, respectively. As the Mo concentration increased from 22 to 32 at.%, the interdiffusion coefficient decreased while the activation energy increased. The growth rate constant of the interdiffusion zone between U-10wt.%Mo versus Mo was also determined and compared to be 104-105 times lower than those of U-10wt.%Mo versus Al and U-10wt.%Mo versus Al-Si systems. Other desirable physical properties of Mo as a barrier material, such as neutron adsorption rate, melting point and thermal conductivity, are also highlighted.

U-Mo alloys are being developed as low-enrichment uranium fuels under the Reduced Enrichment for Research and Test Reactor (RERTR) program. Significant reactions have been observed between U-Mo fuels and Al or Al alloy matrix. Refractory metal Zr has been proposed as barrier material to reduce the interactions. In order to investigate the compatibility and barrier effects between U-Mo alloy and Zr, solid-to-solid U-10wt.%Mo versus Zr diffusion couples were assembled and annealed at 600, 700, 800, 900, and 1000 °C for various times. The microstructures and concentration profiles due to interdiffusion and reactions were examined via scanning electron microscopy and electron probe microanalysis, respectively. Intermetallic phase Mo2Zr was found at the interface, and its population increased when annealing temperature decreased. Diffusion paths were also plotted on the U-Mo-Zr ternary phase diagrams with good consistency. The growth rate of interdiffusion zone between U-10wt.%Mo and Zr was also calculated under the assumption of parabolic diffusion and was determined to be about 103 times lower than the growth rate of diffusional interaction layer found in diffusion couples U-10wt.%Mo versus Al or Al-Si alloy. Other desirable physical properties of Zr as barrier material, such as neutron adsorption rate, melting point, and thermal conductivity, are presented as supplementary information to demonstrate the great potential of Zr as the diffusion barrier for U-Mo fuel systems in RERTR.

U-Mo alloys are being developed as low enrichment uranium fuels under the Reduced Enrichment for Research and Test Reactor (RERTR) Program. In order to understand the fundamental diffusion behavior of this system, solid-to-solid pure U vs Mo diffusion couples were assembled and annealed at 923 K, 973 K, 1073 K, 1173 K, and 1273 K (650 °C, 700 °C, 800 °C, 900 °C, and 1000 °C) for various times. The interdiffusion microstructures and concentration profiles were examined via scanning electron microscopy and electron probe microanalysis, respectively. As the Mo concentration increased from 2 to 26 at. pct, the interdiffusion coefficient decreased, while the activation energy increased. A Kirkendall marker plane was clearly identified in each diffusion couple and utilized to determine intrinsic diffusion coefficients. Uranium intrinsically diffused 5-10 times faster than Mo. Molar excess Gibbs free energy of U-Mo alloy was applied to calculate the thermodynamic factor using ideal, regular, and subregular solution models. Based on the intrinsic diffusion coefficients and thermodynamic factors, Manning’s formalism was used to calculate the tracer diffusion coefficients, atomic mobilities, and vacancy wind parameters of U and Mo at the marker composition. The tracer diffusion coefficients and atomic mobilities of U were about five times larger than those of Mo, and the vacancy wind effect increased the intrinsic flux of U by approximately 30 pct.