ToF-SIMS, XPS and DFT study of the adsorption of 2-mercaptobenzothiazole on copper in neutral aqueous solution and corrosion protection in chloride solution

Abstract

X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) analyses were performed to characterize the interaction of Cu with mercaptobenzothiazole (MBT) in aqueous solution for 1 h and 24 h in absence and presence of NaCl. The fingerprints of the molecules are identified with XPS (S, N and C signals). The analysis of the Cu 2p core level and Auger Cu peaks allow us to show that the Cu metal is covered by a Cu2O oxide layer whose thickness increases with exposure time in the absence of MBT. It is found that MBT forms multilayers on Cu oxide and inhibits the oxide layer growth. The XPS data are consistent with MBT adsorbed on oxide in multilayers, with a small fraction adsorbed on metallic Cu. These interactions are then further characterized using ToF-SIMS. The results suggest adsorption of the MBT molecules in a strongly bonded layer through both S atoms of the organic molecule oriented towards the surface, covered by a weakly bonded multilayer. Quantitative treatments of XPS intensities allows us to evaluate a layer thickness of 23 Å and 32 Å after 1 h and 24 h, respectively. Co-adsorbed water is also identified. The presence of water in the organic layer (ratio H2O/MBT = 0.28) may explain the orientation of the molecules with S directed towards the surface and N interacting through H bonds with water molecules, as suggested by complementary DFT calculations. The adsorption of MBT is similar in presence of NaCl and in pure water, and also inhibits the oxide growth. In addition, MBT adsorption inhibits the adsorption of Cl on the Cu surface. Inductively Coupled Plasma Optical Emission Spectrophotometry (ICP OES) experiments demonstrate that MBT adsorption inhibits Cu dissolution, even after 20 days immersion in NaCl. Thus, we demonstrated that MBT, by adsorbing and forming a full monolayer at the Cu surface, inhibits further oxide growth, Cl adsorption and copper dissolution in NaCl.