Nanocrystallization in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass

The first stages of thermal relaxation towards equilibrium in a Zr 57 Ti 5 Cu 20 Al 10 Ni 8 bulk metallic glass have been studied by differential scanning calorimetry, X-ray diffraction, transmission electron microscopy and high-resolution electron microscopy. These coupled experiments rule out for this glass the existence of a phase separation on the nanometric scale preceding the onset of crystallization. The first step of crystallization is of the primary type, that is it consists of the nucleation of nanocrystallites in the amorphous matrix with which they coexist in metastable equilibrium. The very high nucleation rate leads to a nanometric composite structure with a number density of about 7 2 10 24 m -3 of 3-4nm crystallites, occupying a volume fraction of about 15%. These features, as well as the crystallization kinetics observed during isochronal or isothermal heating, are discussed.     

Effects of Ag and Pd on the nucleation and growth of the nano-icosahedral phase in Zr65Al7.5Ni10Cu7.5M10 (M = Ag or Pd) metallic glasses

The nucleation and growth of a nano-icosahedral phase from a supercooled liquid region of Zr₆₅Al_7.5Ni₁₀Cu_7.5M₁₀ (M = Ag or Pd) glasses have been examined by differential scanning calorimetry and transmission electron microscopy. The growth rate of the icosahedral phase is nearly constant at the initial stage and much slower than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 metallic glass. The homogeneous nucleation rate has a maximum value of 4.4 x 10²⁰ m^-3 s^-1 at 695 K in the Zr₆₅Al_7.5Ni₁₀Cu_7.5Ag₁₀ glass, which is approximately 10² times higher than that for the formation of quasicrystalline phase in the Zr_69.5Al_7.5Ni₁₁Cu₁₂ glass and 10⁴ times higher than that of the Zr₂Ni phase in the Zr₆₅Al_7.5Ni₁₀Cu_17.5 glass. With increasing Pd content, the nucleation rate of the primary phase increases significantly and the growth rate decreases at the crystallization temperature. Thus, the addition of Ag and Pd is effective for an increase in the number of nucleation sites and the suppression of grain growth, which is the main reason for the formation of icosahedral nanoparticles. The significant increase in the nucleation rate is due to an increase in the number of nucleation sites resulting from the short-range ordering consisting of Zr-(Ag or Pd) strong pairs. It is implied that the strong pair Zr-(Ag or Pd) also contributes to the restraint of the long-range rearrangements of the constitutional elements. The formation of the nanoicosahedral phase suggests that icosahedral short-range order exists in the glassy state in the present alloys.