Diffusion of impurity atoms depends on the sublattices occupied, active diffusion mechanisms, and jump frequencies to neighboring sites. The method of perturbed angular correlation of gamma rays (PAC) has been applied over the past decade to study impurity diffusion through measurement of nuclear quadrupole interactions (NQI) at nuclei of 111In/Cd probe atoms. Extensive measurements have been made on highly-ordered compounds having the L12 crystal structure, including In3R, Sn3R, Ga3R, Al3R and Pd3R phases (R= rare-earth element). Measurements in thermal equilibrium at high temperature served to determine lattice locations of 111In parent probe-atoms, through characteristic NQIs, and to measure diffusional jump-frequencies of 111Cd daughter probe-atoms, through relaxation of the NQI. This paper summarizes results of the jump-frequency measurements and relates them to the conventional diffusivity that can be determined, for example, from penetration profiles of tracer species. In spite of chemical similarities of the series of rare-earth phases studied, remarkably large variations in jump frequencies have been observed especially along series of In3R and Pd3R phases. Most phases appear as “line compounds” in binary phase diagrams, but large differences in site-preferences and jump-frequencies were observed for samples prepared to have the opposing limiting phase boundary compositions. Comparisons of jump-frequencies measured at opposing boundary compositions can give insight into the predominant microscopic diffusional mechanisms of the impurity. A change in diffusion mechanism was proposed in 2009 to explain jump-frequency systematics for In3R phases. An alternative explanation is proposed in the present paper based on site-preferences of 111Cd daughter probes newly observed along the parallel Pd3R series. The diffusivity can be expressed as the product of a jump-frequency such as measured in these studies and a correlation factor for diffusion that depends on the diffusion mechanism. The correlation factor can be modeled for the L12 structure and diffusion sublattice of interest using a five-frequency model originally proposed for metals. Although the correlation factor is an essential parameter for the diffusion of impurities, it has never been measured. It is suggested that values of the correlation factor can be determined feasibly by combining results of jump-frequency measurements such as the present ones with diffusivity measurements made for the same host-impurity systems.
Nuclear quadrupole interactions of 111In/Cd solute atoms in a series of rare-earth palladium alloys
