Crack tip chemistry and electrochemistry of environmental cracks in AA 7050

The role of the crack environment in establishing environment-assisted crack (EAC) propagation in AA 7050 alloys is elucidated. A suite of mini-electrodes provided real-time in situ measurements of the crack potential, pH, and chloride concentration during stage II cracking in a chromate–chloride electrolyte under electrochemical control. For material aged to an EAC-susceptible condition, crack growth during an incubation period is characterized by tip polarization to near the applied electrode potential (EApp) and bulk-like chemistry near the crack tip. In contrast, establishment of high-rate crack growth coincided with the development of an acidic, high chloride concentration tip environment and tip depolarization. During steady state high rate crack growth, the tip potential was ∼−0.85VSCE; near-tip potential gradients were ∼1 V/cm. Large ohmic potential drop within fast-growing cracks is indicative of net anodic current in the near tip region and increased mass transport resistance within the crack due to solid corrosion products and/or hydrogen bubble formation. Microinjection of a corrosion-inhibiting or corrosion-promoting solution at the tip suppresses or prompts, respectively, the transition from incubation to high-rate cracking, highlighting the intimate dependence of the crack growth kinetics on the local chemistry. The exceptional EAC resistance of over-aged AA 7050 is intrinsic; injection of an acidic aluminum chloride solution at the tip of a crack of this material while polarized to a high EApp failed to induce brittle crack advance.