Effect of Structural Defects, Surface Irregularities, and Quenched-In Defects on Corrosion of Zr-Based Metallic Glasses

X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) revealed a fully amorphous structure for as-cast bulk metallic glass (BMG) and melt-spun ribbons of Zr₅₂Ti₆Al₁₀Cu₁₈Ni₁₄ prepared by copper mold casting and the melt-spinning technique, respectively. For melt-spun ribbons, the wheel-side surface contained a higher concentration of quenched-in defects (air pockets), whereas surface irregularities were noticed in the air side. Fluctuation microscopy indicated more medium-range order for the as-cast structure of BMG than for the melt-spun ribbon, whereas in the BMG, the medium-range order was located more in the central region than in the periphery. Macro- and microcell electrochemical experiments of the BMG along the cross section and macrocell experiments of each side of the ribbons in dilute acidic chloride environments indicated that the corrosion resistance of the BMG decreased with the increase in the medium-range order; the medium-range order, however, was less deleterious than either the surface irregularities or the quenched-in defects from the viewpoint of corrosion. A surface film formed on the metallic glasses in a dilute acidic chloride environment mainly consisted of oxide of zirconium, in which zirconium was present in the Zr⁺³, Zr⁺², and Zr⁺¹ state in the BMG and in the air-side and wheel-side surfaces, respectively.