Electric field gradients in Zr$_8$Ni$_{21}$ and Hf$_8$Ni$_{21}$ intermetallic compounds; Results from perturbed angular correlation measurements and first-principles density functional theory

TL;DR

This study investigates the electric field gradients in Zr8Ni21 and Hf8Ni21 intermetallics using perturbed angular correlation spectroscopy and density functional theory, revealing phase compositions, site-specific properties, and temperature effects.

Contribution

It provides the first combined PAC and DFT analysis of Zr8Ni21 and Hf8Ni21, identifying phases and site-specific electric field gradients with temperature-dependent behavior.

Findings

Identification of multiple phases including Zr7Ni10 and HfNi3.

Observation of two non-equivalent atomic sites in both compounds.

Temperature-induced changes in electric field gradients at 973 K and 1073 K.

Abstract

Numerous technological applications of Ni-based Zr and Hf intermetallic alloys promoted comprehensive studies in Zr$_8$Ni$_{21}$ and Hf$_8$Ni$_{21}$ by perturbed angular correlation (PAC) spectroscopy, which were not studied earlier until this report. The different phases produced in the samples have been identified by PAC and X-ray diffraction (XRD) measurements. Using $^{181}$Hf probe, two non-equivalent Zr/Hf sites have been observed in both Zr$_8$Ni$_{21}$ and Hf$_8$Ni$_{21}$ compounds. From present PAC measurements in Zr$_8$Ni$_{21}$, a component due to the production of Zr$_7$Ni$_{10}$ by eutectic reaction from the liquid metals is also observed. The phase Zr$_7$Ni$_{10}$, however, is not found from the XRD measurement. In Zr$_8$Ni$_{21}$, while the results do not change appreciably up to 973 K exhibit drastic changes at 1073 K. In Hf$_8$Ni$_{21}$, similar results for the two non-equivalent sites have been found but site fractions are in reverse order. In this alloy, a different contaminating phase, possibly due to HfNi$_3$, has been found from PAC measurements but is not found from XRD measurement. Density functional theory (DFT) based calculations of electric field gradient (EFG) and asymmetry parameter ($\eta$) at the sites of $^{181}$Ta probe nucleus allowed us to assign the observed EFG fractions to the various lattice sites in (Zr/Hf)$_8$Ni$_{21}$ compounds.