Cascading crystallographic transitions and melting curve of elemental zirconium

TL;DR

This study provides a detailed analysis of zirconium's phase transitions and melting behavior under high pressure, revealing new phases and accurately modeling the melting curve with implications for high-pressure physics.

Contribution

It reports the first identification of a bcc-beta prime phase in zirconium and refines the understanding of phase transitions and melting curve modeling under high pressure.

Findings

Discovery of a new bcc-beta prime phase in zirconium.

Accurate modeling of zirconium's melting curve up to high pressures.

Confirmation of bulk moduli through combined P-V EOS and melting data.

Abstract

Precise fitting of the experimental data analyzed separately for each identified crystallographic phase alpha, omega, beta, beta prime and beta double prime yield different bulk moduli Bo and Bo prime and different zero pressure volumes (Vo) than those claimed in the literature. Special attention is given to the bcc phases indicating cascading transitions beta to beta prime to beta double prime associated with volume collapse. The present analysis reveals the existence of a bcc-beta prime phase which is reported here for the first time. It is shown that the first order volume collapse at about 58GPa beta to beta prime is followed by a moderate transition to the bcc-beta double prime phase. The beta prime phase is stable up to 110GPa. Above 110GPa the bcc-beta double prime is dominant and stable up to about 220GPa. The derived bcc-double prime bulk moduli are confirmed by the Lindemann-Gilvarry criterion as Bo and Bo prime simultaneously fit both the P-V EOS and the P-T melting data points (combined approach). The calculated melting curve of elemental Zr, taking into account the thermal pressure Poth shift and the elevated melting Tmo prime at Poth , yield very good fit of the experimental melting data permitting a safe extrapolation to high pressures and temperatures. In addition, the combined approach lead to direct determination of the Greuneisen parameter gammao, needed for applying the approximated Lindemann-Gilvarry melting formula.