Ordering in Ni-Mo alloys - First-principles calculations versus experimental observations

An extensive amount of experimental work has been reported in the literature on the ordering behaviour of Ni-Mo alloys containing 8-33 at% of Mo, which exhibit both short-range and long-range ordering phenomena and a competition among several fee-based long-range ordered structures. We have used local-density-based tight binding linear muffin-tin orbital (TB-LMTO) method in conjunction with 'augmented space recursion + orbital peeling' (ASR + OP) for the determination of ground state energies of these superstructures in terms of effective pair interactions up to the fourth nearest neighbour pairs. The ordering behaviour of the four competing fee-based superstructures has been studied using the mean-field-based 'static concentration wave' (SCW) model in terms of the free energy-order parameter plots (Landau plots) and the free energy-composition plots. The instability domains with respect to concentration fluctuations, both short wavelength (ordering) and long wavelength (clustering) have been identified from these calculations. This information has been used to predict the sequence of transformation events in the Ni-Mo alloys undergoing ordering and/or clustering and the results are compared with those obtained experimentally.