Electric field gradients and phase stability of Zr9Ni11 and Hf9Ni11 intermetallics; perturbed angular correlation (PAC) and first-principles calculations studies

Intermetallic compounds Zr9Ni11 and Hf9Ni11 have been studied by time-differential perturbed angular correlation (TDPAC) spectroscopy. Multiphase components have been found in both these compounds. In Zr9Ni11, the phase Zr9Ni11 is found to be predominant (89%) at room temperature. Besides this, a secondary phase due to Zr8Ni21 is found (11%). From temperature-dependent TDPAC studies, it is found that Zr9Ni11 is unstable at higher temperature (u003e773 K). At 773 K, Zr9Ni11 partially decomposes to Zr7Ni10 and at 973 K, it is completely decomposed to ZrNi and Zr7Ni10. This compositional phase change from Zr9Ni11 to ZrNi and Zr7Ni10 is not reversible and we do not retrieve Zr9Ni11 at remeasured room temperature. In stoichiometric Hf9Ni11, the phase HfNi is found to be predominant (81%) while the phase due to Hf9Ni11 is found as a minor phase (19%). However, no compositional phase change at higher temperature is found in Hf9Ni11. After heating the sample at 873 K, the same two phases of HfNi and Hf9Ni11 have been observed with almost same fractions as found before heating the sample. Similar values of quadrupole frequencies and asymmetry parameters for both Zr9Ni11 and Hf9Ni11 indicate isostructurality of the two phases. X-ray diffraction (XRD) and transmission electron microscopy (TEM)/selected area electron diffraction (SAED) measurements have been carried out in both Zr9Ni11 and Hf9Ni11 to further characterize these compounds and to determine the phase components in these samples. Phase components found from XRD and TEM/SAED measurements are similar to those observed from PAC measurements. Electric field gradients (EFG) at 181Ta impurity atom have been calculated in both Zr9Ni11 and Hf9Ni11 by density functional theory (DFT) using all electron full potential (linearized) augmented plane wave plus local orbitals (FP-(L)APW+lo) method in order to assign the phase components.