| Aluminum-based metallic glasses possess some remarkable attributes that make them appealing for corrosion prevention applications. For example, Al-based glasses are resistant to pitting corrosion and can function as a corrosion barrier film, a sacrificial anode, and provide active corrosion inhibition by releasing alloying elements as inhibiting ions. While the amorphous structure makes these functions possible by allowing a high alloying element content to be achieved in solid solution, it is also a potential weakness because the amorphous structure is metastable. Partial crystallization occurs over time as nanometer-scale, solute-depleted f.c.c. Al precipitates ("nanocrystals") nucleate and grow within a remaining amorphous matrix. There was once some concern that these nanocrystals may serve as pit initiation sites and degrade the good pitting resistance of an amorphous alloy. Contrary to early predictions, this work shows that several partially nanocrystalline Al-based alloys are as corrosion resistant as fully amorphous alloys of the same bulk composition. This thesis provides an in-depth investigation of several mechanisms that can explain the good corrosion resistance of partially nanocrystalline glasses.;The corrosion resistance of the amorphous and partially nanocrystalline glasses was first characterized by examining chloride induced pitting. The results of these experiments guided diagnostic studies of chloride-induced metastable pitting and stable pit growth, alkaline dissolution and passivation behavior, and surface characterization using SEM, TEM, and AFM, all at a sensitivity level tailored to detect nm-scale corrosion processes. These techniques together served as diagnostics to help determine the mechanism by which the corrosion resistance of a partially nanocrystalline Al-based glass may be similar or superior to that of its fully amorphous precursor. The overall conclusion of this dissertation is that Al-based glassy alloys with solute-depleted Al nanocrystals are just as corrosion resistant as their fully amorphous precursors and the most probable explanation is that nanocrystals do not serve as detrimental heterogeneities because they are covered and not sensed by the electrolyte due to a continuous, homogeneous, solute-rich, protective oxide film. It is also clear that pit propagation in the glasses is hindered by the beneficial solutes in solid solution. |
