Saman Hosseinpour

Combined in Situ Quartz Crystal Microbalance with Dissipation Monitoring, Indirect Nanoplasmonic Sensing, and Vibrational Sum Frequency Spectroscopic Monitoring of Alkanethiol-Protected Copper Corrosion

In this study, we have applied three techniques to simultaneously and in situ study the initial stage of corrosion of copper protected by a self-assembled monolayer of octadecanethiol (ODT). We combined quartz crystal microbalance with dissipation monitoring (QCM-D), indirect nanoplasmonic sensing (INPS), and vibrational sum frequency spectroscopy (VSFS) and obtained complementary information about mass uptake and optical and spectroscopic changes taking place during the initial corrosion phase. All three techniques are very sensitive to the formation of a corrosion film (thickness in the range 0-0.41 nm) under mildly corrosive conditions (dry air, <0.5% relative humidity). The three techniques yield information about the viscoelasticity of the corrosion film (QCM-D), the homogeneity of the corrosion reaction on the surface (INPS), and the stability of the ODT protection layer (VSFS). Furthermore, by also studying the corrosion process in humid air (ca. 70% relative humidity), we illustrate how the combination of these techniques can be used to differentiate between simultaneously occurring processes, such as water adsorption and corrosion product formation.

Chemisorbed and Physisorbed Water at the TiO2/Water Interface

The interfacial structure of water in contact with TiO2 is the key to understand the mechanism of photocatalytic water dissociation as well as photoinduced superhydrophilicity. We investigate the interfacial molecular structure of water at the surface of anatase TiO2, using phase-sensitive sum frequency generation spectroscopy together with spectra simulation using ab initio molecular dynamic trajectories. We identify two oppositely oriented, weakly and strongly hydrogen-bonded subensembles of O–H groups at the superhydrophilic UV irradiated TiO2 surface. The water molecules with weakly hydrogen-bonded O–H groups are chemisorbed, i.e. form hydroxyl groups, at the TiO2 surface with their hydrogen atoms pointing toward bulk water. The strongly hydrogen-bonded O–H groups interact with the oxygen atom of the chemisorbed water. Their hydrogen atoms point toward the TiO2. This strong interaction between physisorbed and chemisorbed water molecules causes superhydrophilicity.

Monolayer Study by VSFS: In Situ Response to Compression and Shear in a Contact

Self-assembled octadecyltrichlorosilane ((OTS), CH3(CH2)17SiCl3) layers on hydroxyl-terminated silicon oxide (SiO2) were prepared. The monolayers were characterized with atomic force microscopy (AFM) and contact angle measurements; their conformation was studied before, during, and after contact with a polymer (either PDMS or PTFE) surface using the vibrational sum frequency spectroscopy (VSFS) technique. During contact, the effect of pressure was studied for both polymer surfaces, but in the case of PTFE, the effect of shear rate on the contact was simultaneously studied. The VSFS response of the monolayers with pressure was almost entirely due to changes in the real area of contact with the polymer and therefore the Fresnel factors, whereas sliding caused disorder in the previously all-trans monolayer, as evidenced by a significant increase in the population of gauche defects.

Corrosion Inhibition of Two Brass Alloys by Octadecanethiol in Humidified Air with Formic Acid

Self-assembled monolayers of octadecanethiol (ODT) have previously shown to provide excellent corrosion inhibition on copper exposed to humidified air containing formic acid, mimicking indoor atmospheric corrosion. ODT layers are, however, much less efficient corrosion inhibitors for zinc. In this work, we elucidate the possibility of using ODT monolayers to inhibit corrosion of brass. Based on a quantitative analysis of corrosion products, we found that ODT provides equally good corrosion inhibition of single-phase Cu20Zn as of pure copper, retarding the transportation of corrosion stimulators to the brass surface. On double-phase Cu40Zn, however, local galvanic effects led to less efficient corrosion inhibition and more corrosion products than on Cu20Zn.

Vibrational Spectroscopy in Studies of Atmospheric Corrosion

Vibrational spectroscopy has been successfully used for decades in studies of the atmospheric corrosion processes, mainly to identify the nature of corrosion products but also to quantify their amounts. In this review article, a summary of the main achievements is presented with focus on how the techniques infrared spectroscopy, Raman spectroscopy, and vibrational sum frequency spectroscopy can be used in the field. Several different studies have been discussed where these instruments have been used to assess both the nature of corrosion products as well as the properties of corrosion inhibitors. Some of these techniques offer the valuable possibility to perform in-situ measurements in real time on ongoing corrosion processes, which allows the kinetics of formation of corrosion products to be studied, and also minimizes the risk of changing the surface properties which may occur during ex-situ experiments. Since corrosion processes often occur heterogeneously over a surface, it is of great importance to obtain a deeper knowledge about atmospheric corrosion phenomena on the nano scale, and this review also discusses novel vibrational microscopy techniques allowing spectra to be acquired with a spatial resolution of 20 nm.

Insights into Galvanic Corrosion Behavior of Ti-Cu Dissimilar Joint: Effect of Microstructure and Volta Potential

The effect of microstructure on corrosion behavior of a solid-state explosion welded Ti-Cu bimetal is investigated by means of alternating current-direct current (AC-DC) electrochemical measurements, optical microscopy, scanning electron microscopy, and scanning Kelvin probe force microscopy (SKPFM). The results indicate that the titanium regions in the welding interface, local melted zone (LMZ), and LMZ-Cu interface are potential sites for initiation of corrosion attacks. SKPFM mapping clearly shows that before exposure of the sample to a 3.5% NaCl corrosive solution and at the beginning of the exposure, the Cu side of the bimetal has a higher Volta potential in comparison to that of the Ti region, and thus acts as a cathode. Electrochemical measurements also confirm that titanium acts as an anode and copper as a cathode, in the first moments of immersion, in accordance with macroscopic observations and SKPFM results. However, by growing a passive layer of titanium oxide and titanium hydroxide on the Ti side after about 1 h exposure to the corrosive medium, the titanium side becomes nobler and the polarity arrangement in the galvanic couple reverses.

Publisher's Note: Radiation Induced Corrosion of Copper in Anoxic Aqueous Solution [Electrochem. Solid-State Lett., 15, C5 (2012)]

Erratum to : Radiation Induced Corrosion of Copper in Anoxic Aqueous Solution (vol 15, pg C5, 2012)