Combined in situ microstructural study of the relationships between local grain boundary structure and passivation on microcrystalline copper

TL;DR

This study combines in situ ECSTM and EBSD techniques to explore how different grain boundary structures in microcrystalline copper influence passivation behavior in NaOH solution, revealing structure-dependent passivation efficiency.

Contribution

It provides new insights into the relationship between grain boundary microstructure and passivation, especially the effects of boundary deviation and dislocation density.

Findings

High angle random boundaries form thicker passive films reducing oxidation efficiency.

Sigma3 CSL boundaries show passivation efficiency dependent on boundary deviation angle.

Deviations from ideal CSL boundaries affect local oxidation and passivation behavior.

Abstract

In situ Electro-Chemical Scanning Tunneling Microscopy (ECSTM) and Electron Back-Scatter Diffraction analysis of the same local microstructural region were combined to study the relationships between grain boundary (GB) type and structure and passivation on microcrystalline copper in 0.1 M NaOH aqueous solution. The results show that, for high angle random boundaries, passivation in the Cu(I) oxidation range is characterized by a decrease of the depth of GB edge region due to the formation of a passive film locally thicker than on the adjacent grains and thus to anodic oxidation being locally less efficient since it consumes more copper at the grain boundaries. For sigma3 CSL boundaries, the Cu(I) passivation efficiency was observed to be dependent on the local structure of the boundaries. A transition from more to less efficient passivation was observed for a deviation angle of 0.4-0.5{\deg} of the {111} GB plane with respect to the perfect geometry of an ideal coherent twin boundary. This transition would result from the effect on the local anodic oxidation properties of an increased density of misfit dislocations accommodating the increased deviation of the boundary plane from the exact CSL plane.