In situ investigations of the metal/atmophere interface

Abstract: This thesis presents a new experimental setup for surfaceanalysis studies, incorporating chemical information frominfrared reflection absorption spectroscopy (IRAS) andquantitative information from quartz crystal microbalance(QCM). The integrated IRAS/QCM surface analysis system enablesin situstudies to be conducted of the metal/atmosphereinteraction on a sub-monolayer level. In combination withtopographical information from tapping mode atomic forcemicroscopy (TM-AFM), it was possible to follow the formation ofcorrosion products providing information about chemicalidentity, quantity and lateral distribution. The newlydeveloped system was used to study the influence of relativehumidity (RH) and levels of sulfur dioxide (SO2), ozone (O3)and nitrogen dioxide (NO2) down to concentrations of subparts-per-million (ppm), on the initial stages of atmosphericcorrosion of copper.Exposure to RH led to the formation of small grains ofcuprous oxide (Cu2O), with an average diameter of approximately40 nm. The grain nucleation rate increased with increasing RHdue to the increasing amount of physisorbed water on thesurface.Exposure to RH and SO2 led to the formation of coppersulfite (CuSO3•xH2O) species as well as reduction in therate of Cu2O formation. The formation of CuSO3•xH2Ooccurred through the dissolution and consecutive precipitationof surface-bound copper sulfite complexes.The roles of O3 and NO2 in the SO2-induced atmosphericcorrosion of copper was also investigated. O3 was found to havea two-fold effect, resulting in the oxidation of the coppersulfite species to copper sulfate and the enhancement of Cu2Oformation. NO2 promoted the oxidation of copper sulfitespecies, though less efficiently than O3, and reduced Cu2Oformation. In addition, copper nitrate formation wasobserved.IRAS was also used to investigate the interaction betweenSO2 and surfaces made of platinum and palladium. Sulfuric acidformation was observed on both metals, showing the importanceof the surface on the formation of the metal/atmospherereaction products.Keywords:Atmospheric corrosion, IR-spectroscopy, IRAS,QCM, AFM, SO2, O3, NO2, Cu.