CALPHAD modeling and ab initio calculations of the Np-U-Zr system

TL;DR

This study develops a thermodynamic CALPHAD model and performs ab initio DFT calculations to better understand the phase diagram of the complex Np-U-Zr nuclear fuel system, highlighting uncertainties and improvements.

Contribution

It introduces a combined CALPHAD and DFT approach to model the Np-U-Zr system, providing initial phase diagram insights and refining ab initio enthalpy predictions.

Findings

CALPHAD model reasonably reproduces high-temperature phases

DFT + U reduces enthalpy overestimation compared to standard DFT

Further work needed for a complete phase diagram

Abstract

Phase diagram of Np-U-Zr, a key ternary alloy system of relevance for metallic nuclear fuels, is still largely undetermined. Here a thermodynamic model for the Np-U-Zr system is developed based on Muggianu extrapolation of our models for the U-Zr, Np-Zr, and Np-U binary systems, all employing the CALculation of PHAse Diagrams (CALPHAD) method. This model reproduces available experimental data for the high temperature phases reasonably well, but is uncertain for the lower temperature phases for which experimental data are scarce. Ab initio calculations are performed on the BCC phase of the Np-U-Zr system at 28 compositions employing density functional theory (DFT) both in its standard form and the so-called DFT plus Hubbard U (DFT + U) modification. When referencing to our CALPHAD model, standard DFT on average overestimates the enthalpy of mixing of the BCC phase by 0.093 eV/atom, while DFT + U reduces the error to 0.009-0.036 eV/atom when the effective Hubbard U parameters are in the ranges of single-structure optimized Ueff's determined in our previous studies of the Np-Zr and U-Zr systems (0.65-0.90 for Ueff(Np) and 0.99-1.49 eV for Ueff(U), respectively). Our combined CALPHAD and ab initio modeling provides an initial attempt to determine the phase diagram of the Np-U-Zr system but further work is needed for a reliable determination.