The Early-Stage Corrosion of Copper Materials in Chloride and Sulfide Solutions: Nanoscale Characterization and The Effect of Microstructure

Abstract

The microstructures of copper (Cu) materials were investigated by electron backscatter diffraction, showing that electrodeposited (ED) Cu has a homogenous polycrystalline microstructure, while cold spray (CS) Cu has a heterogeneous microstructure with varying grain size, pores, and interfacial splat regions. The corrosion rate was examined by corrosion potential (E CORR ) and polarization resistance (R p ) measurements on Cu specimens in solutions containing 0.1 M NaCl + 1 × 10 −3 M Na 2 S. Although the as sprayed CS-Cu was the least corrosion resistant, the corrosion rate of the heat-treated CS-Cu was similar to that of the ED-Cu and wrought Cu (SKB-Cu). Electrochemical behaviours of Cu materials were investigated by either a potentiodynamic scan or a potentiostatic polarization at a more positive potential (E > E CORR ) for various experiment durations up to 4 h, showing that the heat-treated CS-Cu, SKB-Cu and ED-Cu exhibited very similar behaviour while the as sprayed CS-Cu showed erratic behavior consistent with a variable surface reactivity. Nanoscale scanning transmission electron microscopy analysis has been performed at the cross-section of an anodically-oxidized CS-Cu specimen, revealing a two-layer film structure, mostly composed of Cu sulfide, with a minor diffusion of sulfur in the local area of an interfacial splat boundary tip.