Molecular studies of initial atmospheric corrosion of copper Exploration of ultra-sensitive techniques for the inhibiting effect of self assembled monolayers, and the effect of gamma radiation

Abstract: Atmospheric corrosion indoors is of great practical importance for the degradation of metals, for example in electronics, military equipment, and cultural heritage items. It involves a wide range of chemical, electrochemical, and physical processes occurring in gas, liquid, and solid phases, and at the interfaces between them. Hence, a molecular understanding of the fundamental interactions during atmospheric corrosion is of utmost importance.Copper is one of the most used metals in electrical contacts, power generators, heat exchangers, etc. and is prone to indoor atmospheric corrosion. Although corrosion and oxidation of copper in the presence of corrosion stimulators is thermodynamically inevitable, there are ways to reduce the kinetics of corrosion and oxidation reactions.Self assembled monolayers (SAMs) of organic molecules, when adsorbed on copper surfaces, have proven to be efficient barriers against copper corrosion. However, understanding at the molecular level of the initial stages of corrosion of SAM covered copper in atmospheric corrosion conditions is lacking. The main reason is the inability of the conventional analytical methods to detect and characterize very thin corrosion products formed during the initial stages (from seconds to days) of atmospheric corrosion of SAM covered copper. To overcome this situation a highly surface sensitive technique, vibrational sum frequency spectroscopy (VSFS), has been utilized in situ and ex situ in this thesis to detect and follow the oxidation of alkanethiol SAM covered copper in dry air as well as to assess the conformational changes of SAM molecules during oxidation.  A very sensitive gravimetric method, quartz crystal microbalance with dissipation monitoring (QCM-D), and a highly sensitive and versatile optical technique, nanoplasmonic sensing (NPS), were combined in situ with VSFS to quantify this very slow oxidation process. This combination allowed the heterogeneity of the oxidation process as well as the mass and the rigidity of the corrosion products to be detected simultaneously.To address indoor atmospheric corrosion conditions where carboxylic acids play an important role we next studied the interaction between SAM covered copper and humidified air, to which formic acid was added. The in situ identification of the corrosion products and their formation kinetics was done using near surface sensitive infrared reflection/absorption spectroscopy (IRAS), and the effect of hydrocarbon chain length in alkanethiol SAMs on their corrosion protection efficiency was investigated. The effect of the anchoring group in the SAMs on their corrosion protection efficiency was studied for hexaneselenol using -SeH as the anchoring group, and the results were compared with its thiol counterpart, hexanethiol, with -SH as the anchoring group. Complementary in situ and ex situ VSFS measurements were performed to assess the quality of the SAMs before, during, and after exposure.It was shown that the SAMs of alkanethiols greatly inhibited the formation of copper (I) oxide and slowed down the formation of other corrosion products, i.e. copper formate and copper hydroxid. This was due to a selective hindrance of the corrosion stimulators, oxygen, water, and formic acid molecules reaching the copper-SAM interface. The corrosion inhibiting effect increased with the hydrocarbon chain length. The SAMs of hexaneselenols, on the other hand, exhibited an accelerated formation of copper (I) oxide, copper formate and copper hydroxide compared to an unprotected surface as a result of the partial removal of hexaneselenol molecules from the copper surface during prolonged exposure.The experience gained in characterizing and quantifying thin copper oxides was further used to explore the influence of gamma (?) radiation on copper corrosion in anoxic water. This multi-analytical approach included IRAS, cathodic reduction, confocal Raman microscope, atomic force microscopy, scanning electron microscopy, x-ray photoelectron spectroscopy, and inductively coupled plasma - atomic emission spectroscopy. The results clearly showed that copper dissolution as well as the oxide layer thickness increase with gamma radiation under the exposure conditions.