Compositional Glass: A State with Inherent Chemical Disorder, Exemplified by Ti-rich Ni3(Al,Ti)1 D024 Phase

Abstract

A compositional glass is a state with an unavoidable disorder in chemical compositions on each site, characterized by frustration and freezing of the compositional degrees of freedom at low temperature. From this state a full atomic long-range order is unachievable by a reasonable thermodynamic treatment. There is a similarity between a spin glass (a magnetic state with disorder in spin orientations) and a compositional glass (with disorder in site occupations by chemical elements): both have frustrated ground states and a frozen disorder at low temperatures T < Tf (here Tf is called the freezing temperature). While it is possible to perform a ground-state search in a compositional glass, the resulting set of the fully ordered structures does not adequately represent the real solid with an inherent atomic disorder. Compositional glasses constitute a class of materials, which is insufficiently understood, but is of high industrial importance. Some of the phases in the precipitated alloys (including steels, high-entropy alloys, and superalloys) might be compositional glasses, and their better understanding would facilitate materials design. Due to their strength at high operating temperatures, superalloys are used in combustion engines and particularly in jet turbine engines. Precipitation strengthening of nickel superalloys is an area of active research. Local phase transformations inside Ni3Al-based precipitates are of particular interest due to their impact on creep strength. In the Ni3(Al1−xTix)1 ternary system, the competing phases are Ni3Al-type L12 (γʹ) and Ni3Ti-type D024 (η), while D019 (χ) is higher in energy. These three phases differ by the stacking of atomic layers: locally, the last two look like the internal and external stacking faults in L12. We compute enthalpies of disordered and ordered Ni3(Al1−xTix)1 ternary structures, examine phase stability, investigate the ground states and competing structures, and predict that the Ti-rich Ni3(Al1−xTix)1 D024 phase is a compositional glass with the atomic disorder on the Al/Ti sublattice. To resolve apparent contradictions among the previous experiments and to confirm our prediction, we perform X-ray diffraction and scanning electron microscopy analysis of the cast Ni3(Ti0.917Al0.083)1 sample. Our measurements appear to confirm the ab initio computed results. Our results elucidate properties of compositional glasses and provide a better understanding of precipitation strengthening mechanisms in Ni superalloys.