The conditions of formation and stability of quasi-crystalline phases in aluminum-manganese alloys

The conditions of formation, stability, and thermodynamic properties of the icosahedral and decagonal quasi-crystalline phases in the Al-Mn system were studied experimentally. The thermodynamic properties of equilibrium crystalline Al-Mn compositions over the composition and temperature ranges 0–26 at % Mn and 628–1193 K, respectively, and of melts over wide temperature and composition ranges (1043–1670 K and 0–50.1 at % Mn) were determined. Measurements were made by the integral variant of the effusion method under the conditions of an ultrahigh oilless vacuum and Knudsen mass spectrometry. An original technique based on the initiation and study of equilibria in reactions of the alloys with special admixtures of sodium or magnesium fluorides with the formation of volatile products was used to extend the interval of measurements to low temperatures. Complete, reliable, and consistent data on the thermodynamic properties of icosahedral and decagonal quasi-crystalline and crystalline phases based on aluminum and Al-Mn melts were obtained for the first time. Al-Mn melts were shown to contain associates of three types, AlMn, Al₂Mn, and Al₅Mn. The contributions of covalent interactions to the Gibbs energy and enthalpy of mixing was found to be by far predominant. The thermodynamic properties of alloys of the same chemical composition in the quasi-crystalline and equilibrium crystalline states were compared. The decagonal phase was found to be more stable than icosahedral quasi-crystals. The difference of the Gibbs energies of quasi-crystals of the two types and crystalline compositions increased as the temperature lowered. Arguments in favor of the entropy nature of the stabilization of quasi-crystals were obtained. These phases, like metallic glasses, are only an intermediate state between liquids and crystals and cannot be ground stable alloy states. The conditions of obtaining quasi-crystalline phases from melts were found to be controlled by the appearance of a substantial fraction of icosahedral short-range order in liquids in the region of compositions where associates of a certain kind (Al₅Mn) were formed in substantial amounts, x(Al₅Mn) ≥ 0.11.