The effect of ion beam mixing of nickel-aluminum alloys with 500 keV krypton ions has been investigated over a range of temperature, composition, ion dose, and post-irradiation thermal treatments. Samples were formed by aternate evaporation of layers of aluminum and nickel. A portion of these samples was subsequently annealed to form intermetallic compunds. Irradiations were performed at both room temperature and 80 K using the 2 MV ion accelerator at Argonne National Laboratory. Phase transformations were observed during both in situ irradiations in the High Voltage Electron Microscope(HVEM) at Argonne and also in subsequent analysis of an array of irradiated samples. Electron diffraction indicates the presence of metastable crystalline structures not present in the conventional nickel-aluminum phase diagram. Transformations occur at doses as low as 5×1014 cm−2 and continue to develop as the irradiation progresses up to 2×l016 cm−2. Layer mixing is followed through Rutherford Backscattering analysis. Samples are also checked with x-rays and Electron Energy Loss Spectroscopy (EELS). A thermodynamic argument is presented to explain the phase transformations in terms of movements on a free energy diagram. This analysis explains the interesting paradox concerning the radiation hardness of the NiAl[l] phase and the amorphous structure of mixed Ni-50% Al layers[2].