New zirconium hydrides predicted by structure search method based on first principles calculations

TL;DR

This study used structure search methods based on first principles calculations to predict and analyze the stable crystal structures of zirconium hydrides at various hydrogen concentrations, providing insights into phase stability and transitions relevant to reactor materials.

Contribution

The paper introduces a novel stable P3m1 ZrH0.5 structure and revisits the stability of other ZrH phases using first principles calculations and thermal simulations.

Findings

Discovered a new stable P3m1 ZrH0.5 structure.

Identified temperature-dependent stability of ZrH phases.

Revealed phase transition pathways influenced by cooling rates.

Abstract

The formation of precipitated zirconium (Zr) hydrides is closely related to the hydrogen embrittlement problem for the cladding materials of pressured water reactors (PWR). In this work, we systematically investigated the crystal structures of zirconium hydride (ZrHx) with different hydrogen concentrations (x = 0~2, atomic ratio) by combining the basin hopping algorithm with first principles calculations. We conclude that the P3m1 {\zeta}-ZrH0.5 is dynamically unstable, while a novel dynamically stable P3m1 ZrH0.5 structure was discovered in the structure search. The stability of bistable P42/nnm ZrH1.5 structures and I4/mmm ZrH2 structures are also revisited. We find that the P42/nnm (c/a > 1) ZrH1.5 is dynamically unstable, while the I4/mmm (c/a = 1.57) ZrH2 is dynamically stable.The P42/nnm (c/a < 1) ZrH1.5 might be a key intermediate phase for the transition of {\gamma}->{\delta}->{\epsilon} phases. Additionally, by using the thermal dynamic simulations, we find that {\delta}-ZrH1.5 is the most stable structure at high temperature while ZrH2 is the most stable hydride at low temperature. Slow cooling process will promote the formation of {\delta}-ZrH1.5, and fast cooling process will promote the formation of {\gamma}-ZrH. These results may help to understand the phase transitions of zirconium hydrides.