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The initiation of intergranular corrosion at various types of grainboundaries (GBs) was studied at the nanometer scale on microcrystalline copperin 1 mM HCl aqueous solution. In situ Electrochemical Scanning TunnelingMicroscopy (ECSTM) and Electron Back-Scatter Diffraction analysis of the samelocal microstructural region were combined using an innovative methodologyincluding micro marking performed with the STM tip. The results demonstratethat electrochemically-induced intergranular dissolution, at the surfacetermination of GBs, is dependent on the grain boundary character. It is foundthat random high angle boundaries as well as sigma9 coincidence site lattice(CSL) boundaries are susceptible to nanoscale initiation of intergranularcorrosion while for sigma3 CSL boundaries the behavior is dependent on thedeviation angle of the GB plane from the exact orientation. For the sigma3twins, a transition from resistance to susceptibility occurs between 1{\deg}and 1.7{\deg} of deviation as a result of the increase of the density of steps(i.e. misorientation dislocations) in the coincidence boundary plane. The workemphasizes the precision needed in the design of the grain boundary network inapplications where intergranular corrosion or its initiation must be controlledat the nanoscale.

Nanoscale Intergranular Corrosion and Relation With Grain Boundary Character as Studied In Situ on Copper