Roles of Chloride Ions in the Formation of Corrosion Protective Films on Copper

Unambiguous evidence is presented that the chloride ions play a dual role in the formation of a micrometre thick film of polymerized [Cu-Cl-MBI] n . This occurs when the copper is exposed to 3 wt.% NaCl solution containing 1 mM of mixture of inhibitors 2-mercaptobenzimidazole, MBI, and octylphosphonic acid, OPA, in the molar ratio MBI:OPA of 9:1. The chloride ions act simultaneously as a promoter of polymerized [Cu–MBI] n /[Cu–Cl–MBI] n film formation and a reactant that is incorporated in the film, as confirmed by time-of-flight secondary ion mass spectrometry. Also, formation of a Cu 2 O film under the Cu-inhibitor film was proven by focused ion beam microscopy, with chemical analysis being employed at the cross-section of the thick polymerized film. The Cu(I) oxide underlayer, together with the porous straw-like morphology of the [Cu–Cl–MBI] n overlayer, is believed to be responsible for the excellent corrosion protection of copper, even in a chloride environment without the reservoir of MBI+OPA. We also report a new insight into the mechanism of degradation of the Cu–MBI/Cu–Cl–MBI film that results in the formation of (MBI) 2 dimers. The inhibitor layer, formed in NaCl solution and containing the synergistic combination of MBI and OPA, showed outstanding resistance to degradation.