Corrosion effects on copper exposed in a humid atmosphere with formic acid (mimicking indoor corrosion) have been explored through successive increase in surface lateral resolution from macroscale (IRRAS, GIXRD) over microscale (LOM, SEM, IR microscopy) to nanoscale (Nano-FTIR, FIB/SEM/EDS). Initial more uniform growth of Cu2O is followed by more varying topography and thickness until local removal of Cu2O enables the aqueous adlayer to react with the copper substrate. Local formation of Cu(OH)(HCOO) and adjacent Cu2O provide microscopic and spectroscopic evidence of corrosion cells. Nano-FTIR shows that the density of Cu(OH)(HCOO) nuclei, but not their size, increases with exposure time.

The corrosion inhibition of self-assembled octadecylphosphonic acid (ODPA) layers on non-oxidized and pre-oxidized copper and Langmuir-Blodgett deposited ODPA layers on pre-oxidized copper was investigated under a simulated indoor atmospheric corrosion environment containing 80% RH and 100 ppb formic acid. The corrosion process was monitored in-situ with infrared absorption/reflection spectroscopy, and the corrosion products were further characterised by grazing incidence X-ray diffraction. Nano-FTIR microscopy was used to reveal the nature, size, and distribution of the corrosion products on the nanoscale. The combination of pre-formed cuprite and ODPA layers, both with only some nanometres thickness, provided an excellent protection under this environment.

The mechanisms of bacterial contact killing induced by Cu surfaces were explored through high-resolution studies based on combinations of the focused ion beam (FIB), scanning transmission electron microscopy (STEM), high-resolution TEM, and nanoscale Fourier transform infrared spectroscopy (nano-FTIR) microscopy of individual bacterial cells of Gram-positive Bacillus subtilis in direct contact with Cu metal and Cu5Zn5Al1Sn surfaces after high-touch corrosion conditions. This approach permitted subcellular information to be extracted from the bioinorganic interface between a single bacterium and Cu/Cu5Zn5Al1Sn surfaces after complete contact killing. Early stages of interaction between individual bacteria and the metal/alloy surfaces include cell leakage of extracellular polymeric substances (EPSs) from the bacterium and changes in the metal/alloy surface composition upon adherence of bacteria. Three key observations responsible for Cu-induced contact killing include cell membrane damage, formation of nanosized copper-containing particles within the bacteria cell, and intracellular copper redox reactions. Direct evidence of cell membrane damage was observed upon contact with both Cu metal and Cu5Zn5Al1Sn surfaces. Cell membrane damage permits copper to enter into the cell interior through two possible routes, as small fragmentized Cu2O particles from the corrosion product layer and/or as released copper ions. This results in the presence of intracellular copper oxide nanoparticles inside the cell. The nanosized particles consist primarily of CuO with smaller amounts of Cu2O. The existence of two oxidation states of copper suggests that intracellular redox reactions play an important role. The nanoparticle formation can be regarded as a detoxification process of copper, which immobilizes copper ions via transformation processes within the bacteria into poorly soluble or even insoluble nanosized Cu structures. Similarly, the formation of primarily Cu(II) oxide nanoparticles could be a possible way for the bacteria to deactivate the toxic effects induced by copper ions via conversion of Cu(I) to Cu(II).

Copper (Cu) has been utilised by humans for millenniums and has become an indispensable metal in modern industry and in our infrastructure. However, corrosion, as a natural process for metallic materials, takes place on copper surfaces in most environments. Thus, understanding corrosion and corrosion protection of copper is of utmost importance to maintain its performance and prolong the lifetime of the applications. Corrosion has been revealed to start from local weak areas of the copper surface. However, the corrosion initiation and propagation mechanism on copper on a molecular level are far from clear.

In this thesis, the corrosion initiation of copper under a simulated indoor atmosphere where formic acid and humidity are present was studied. The corrosion process was monitored in-situ, and the formed corrosion products were characterised on the macro-, micro-, and nanoscale by various analytical techniques from both horizontal and vertical directions of the corroded surfaces. The localised dissolution and formation of the Cu2O layer on narrowly separated areas on the nanoscale were observed both microscopically and spectroscopically. A novel technique, nano infrared spectroscopy (nano-FTIR), was used to probe the formed corrosion products on the nanoscale. Due to the novelty of nano-FTIR, only a few studies in corrosion science using this technique were reported. Thus, this thesis also shows the capability of employing nano-FTIR in corrosion studies.

The ability of ultrathin organic films to protect copper under indoor atmospheres was also studied in this thesis. The main focus was on octadecylphosphonic acid (ODPA), for which the self-assembly process was examined in detail. A multilayer formation of ODPA on copper was observed under the self-assembly deposition, and the thickness of ODPA films increased with the deposition time. The reason for forming multilayers was attributed to the Cu+ ion release during the deposition, resulting in the formation of a Cu+-ODPA complex. The protective ability of these self-assembled ODPA films as well as Langmuir-Blodgett (LB)-deposited films on non-oxidised and pre-oxidised copper was examined under the same exposure conditions as for the unprotected copper. A remarkable ability to protect the surface was observed for the self-assembled and LB-deposited ODPA films on pre-oxidised copper.

Koppar har använts av människor i tusentals år och är numera en ovärderlig metall iden moderna industrin och i många samhällsfunktioner. Korrosion, som är en naturlig process för metaller, är dock något som påverkar koppar i de flesta miljöer, varvid dess egenskaper kan försämras. Det är därför av yttersta vikt att i detalj förstå hur koppar korroderar och även hur koppar kan skyddas för att säkerställa dess funktion och för att förlänga livslängden i applikationer där koppar används. Det är känt att korrosion börjar lokalt i svaga punkter på ytan, men hur korrosionen initieras och fortgår är långt ifrån klart på nanonivå.

I denna avhandling har korrosion av koppar som utsatts för en simulerad inomhusmiljö bestående av fuktig luft och myrsyra studerats. Korrosionsprocessen studerades in-situ och korrosionsprodukterna undersöktes med ett flertal olika analytiska instrument på flera nivåer, från makro-, via mikro-, till nanoskopisk nivå och både i horisontell och vertikal riktning. Såväl den lokala upplösningen som skapandet av lager av Cu2O i smala separerade områden studerades på nanonivå med både mikroskopi och spektroskopi. Den nya tekniken ”Nano-FTIR”, som bara har använts i ett fåtal korrosionsstudier tidigare, användes för att studera korrosionsprodukterna på nanonivå. Ett mål med avhandlingen var därför att visa möjligheterna med denna teknik för korrosionsstudier.

Förmågan hos ultratunna organiska filmer att skydda koppar mot inomhuskorrosion studerades i denna avhandling. Huvudfokus låg på oktadecylfosfonsyra (ODPA), för vilken självassocieringsprocessen även studerades i detalj. Under självassocieringsprocessen på kopparytan skapades ett multilager, vars tjocklek ökade med deponeringstiden. Bildandet av detta multilager förklarades genom en mekanismdär Cu+joner frisattes och bildade komplexet Cu+ - ODPA. Förmågan att skydda ickeoxiderade och föroxiderade kopparytor från korrosion under samma betingelser som den oskyddade kopparn undersöktes för dessa självassocierade filmer och även för ODPA-filmer deponerade med Langmuir-Blodgett (LB)-tekniken. Både de självassocierade filmerna och LB-filmerna på föroxiderad koppar uppvisade en enastående förmåga att förhindra korrosionen.

Hypothesis: The self-assembly of amphiphilic molecules onto solid substrates can result both in the formation of monolayers and multilayers. However, on oxidized and non-oxidized copper (Cu), only monolayer formation was reported for phosphonic acids possessing one phosphate head group. Here, the adsorption of octadecylphosphonic acid (ODPA) on Cu substrates through a self-assembly process was investigated with the initial hypothesis of monolayer formation. Experiments: The relative amount of ODPA adsorbed on a Cu substrate was determined by infrared reflection/absorption spectroscopy (IRRAS) and by atomic force microscopy (AFM) investigations before and after ODPA deposition. X-ray photoelectron spectroscopy (XPS) with sputtering was used to characterize the nature of the layers. Findings: The results show that the thickness of the ODPA layer increased with deposition time, and after 1 h a multilayer film with a thickness of some tens of nm was formed. The film was robust and required long-time sonication for removal. The origin of the film robustness was attributed to the release of Cu ions, resulting in the formation of Cu-ODPA complexes with Cu ions in the form of Cu(I). Preadsorbing a monolayer of octadecylthiol (ODT) onto the Cu resulted in no ODPA adsorption, since the release of Cu(I) ions was abolished.

In this perspective article, the novel technique "nano infrared microscopy" is introduced as a valuable tool in the field of corrosion science to obtain chemical information with a spatial resolution of around 10 nm. Accordingly, the resolution is well below the diffraction limit, in contrast to conventional vibrational microscopy techniques. Thus, studies of corrosion initiation, localized corrosion, and thin protective films can be performed in greater detail than before. There are a few different types of nano infrared microscopes, but they all have in common that they are based on a combination of infrared (IR) spectroscopy and atomic force microscopy (AFM). In this article the theory of the different techniques is discussed, and some results are highlighted to show the ability of the technique in the field of corrosion science. Future possibilities of the technique in studies of corrosion and degradation of materials are also discussed.