Ab initio calculations for void swelling bias in $\alpha$ and $\delta$-plutonium

TL;DR

This study uses DFT calculations to analyze defect properties in alpha and delta phases of plutonium, revealing phase-dependent differences in void swelling bias and implications for irradiation-induced material behavior.

Contribution

It provides the first detailed defect formation energies and volumes in plutonium phases, linking electronic structure effects to swelling bias predictions.

Findings

Defects in delta-Pu have small formation volumes, unlike most metals.

Alpha-Pu exhibits large defect formation volumes, contrary to expectations.

Swelling bias is small in delta-Pu but potentially large in alpha-Pu, affecting irradiation response.

Abstract

Void swelling can develop in materials under persistent irradiation when non-equilibrium vacancy and self-interstitial populations migrate under sufficiently asymmetric interaction biases. In conventional metals, the propensity is determined to first approximation by comparing point-defect relaxation strains. We thus present DFT-based calculations of structures and formation energies and volumes of point defects in the $\alpha$ and the $\delta$-phases of plutonium. Our results show that lattice defects in $\delta$-Pu, in contrast to most fcc metals, have surprisingly small formation volumes. Equally unexpected are the large defect formation volumes found in the low-symmetry $\alpha$-Pu phase. Both these unusual properties can be satisfactorily explained from defect-induced spin/orbital moment formation and destruction in the Pu phases. When we use the calculated defect properties to estimate the classic void swelling bias in each of the phases, we find it to be unusually small in $\delta$-Pu, but likely much larger in $\alpha$-Pu. Hence, swelling rates and mechanisms can diverge dramatically between the different phases of Pu. Especially in the transient regime before formation of large defect clusters, the swelling rate of $\alpha$-Pu can reliably be expected to be much larger than $\delta$-Pu. However, accurate forecasts over longer times will require the conventional void-swelling theory to be modified to handle the complexities presented by the different Pu phases. As a case in point, we show possible anomalous temperature dependence of vacancy properties in $\delta$-Pu, caused by entropic contributions from defect-induced spin-lattice fluctuations. Such complications may affect defect-defect interactions and thus alter the void swelling bias.