Photo-electrochemical analysis of passive film formed on X80 pipeline steel in bicarbonate/carbonate buffer solution

Photo-electrochemical measurement was used to explore the formation potential, formation time, chloride ions concentration, applied potential and pH value of the solution on the electronic property of passive film formed on X80 pipeline steel in 1 M NaHCO₃/0.5 M Na₂CO₃ buffer solution. The results showed that the photocurrent is positive, indicating an n-type semiconductor character of the passive film, the photocurrent increased with increasing the formation potential, prolonging the formation time, decreasing chloride ions concentration, rising applied potential and decreasing the pH value of the solution. Capacitance measurement exhibited a positive slope of Mott-Schottky plot, and the slopes of Mott-Schottky plots increased with the increasing formation potential, showing a decrement of the donor density of the passive film.     

Failure of thin films: Optical shearography versus electrochemical impedance spectroscopy

In the present work, the temperature versus thermal deformation (strain) with respect to time, of different coating films, was studied by a non-destructive technique (NDT) known as shearography. An organic coating, i.e., ACE Premium Enamel, on a metallic alloy, i.e., a carbon steel, was investigated at a temperature range simulating the severe weather temperatures in Kuwait, especially between the daylight and the nighttime temperatures, 20-60 °C. The investigation focused on determining the in-plane displacement of the coating, which amounts to the thermal deformation (strain) with respect to the applied temperature range. Furthermore, the investigation focused on determining the thermal expansion coefficients of coatings, the slope of the plot of the thermal deformation (strain) versus the applied temperature range. In other words, one could determine, from the decreasing value of the thermal expansion coefficients of coatings, a critical (steady state) value of the thermal expansion coefficients of coatings, in which the integrity of the coatings can be assessed with respect to time. In fact, determination of the critical (steady state) value of the thermal expansion coefficients of coatings could be accomplished independent of parameters, i.e., ultraviolet (UV) exposure, humidity, and exposure to chemical species, which normally are considered in conventional methods of assessing the integrity of coatings. Furthermore, results of shearography indicate that the technique is a very useful NDT method not only to determine the critical value of the thermal expansion coefficients of different coatings but also to be used as a 2D-microscope for monitoring the deformation of the coatings in real time at a submicroscopic scale. Also, the obtained data of the shearography technique were compared with data obtained by electrochemical impedance spectroscopy (EIS) in an aqueous solution of 3% NaCl.     

Establishment of equivalent circuits from electrochemical impedance spectroscopy study of corrosion inhibition of steel by pyrazine in sulphuric acidic solution

This paper describes the use of the electrochemical impedance spectroscopy technique (EIS) in order to study the corrosion inhibition process of steel in 0.5 M H₂SO₄ solution at the open circuit potential (OCP). Diethyl pyrazine-2,3-dicarboxylate (Prz) as a non-ionic surfactant (NS) inhibitor has been examined. The Nyquist diagrams consisted of a capacitive semicircle at high frequencies followed by a well-defined inductive loop at low frequency values. The impedance measurements were interpreted according to suitable equivalent circuits. The results obtained showed that the Prz is a good inhibitor. The inhibition efficiency increases with an increase in the surfactant concentration to attain 80% at the 5 × 10⁻³M. Prz is adsorbed on the steel surface according to a Langmuir isotherm adsorption model.     

Local electrical characteristics of passive films formed on stainless steel surfaces by current sensing atomic force microscopy

A current sensing atomic force microscope was used to study the topography and the local electronic properties of the passive film formed on a duplex ferrite-austenite stainless steel (Uranus 50). Comparison of current maps with topography AFM images reveals that the passive film covering austenite and ferrite phases exhibits different properties. On freshly formed passive film, a high and homogenous resistance (typically 10 GΩ for 1 V) characterises the film on austenite grains while current maps of the passive layer covering the ferrite grains show a high density of spots (few 100 MΩ for 1 V). Besides the current maps, local I-V curves acquired on austenite show wider band gap energy than the ones obtained on ferrite grains. Finally, the conductivity difference in passive films covering ferrite and austenite grains is discussed.     

Holographic interferometry as electrochemical emission spectroscopy of carbon steel in seawater with low concentration of RA-41 corrosion inhibitor

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of carbon steel in blank seawater and with seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion test (EI) spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of RA-41 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which were obtained from the EI spectroscopy. Consequently, holographic interferometric is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

Electrochemical, morphological and microstructural characterization of carbon film resistor electrodes for application in electrochemical sensors

The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 Ω and 2.0 kΩ nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 Ω carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN)₆^3−/4− obtained. The 1.5 Ω resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 Ω and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 Ω resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 kΩ resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films.     

Characterisation of alkyl-functionalised Si(1 1 1) using reflectometry and AC impedance spectroscopy

The past few years have seen a dramatic increase in the study of organic thin-film systems that are based on silicon-carbon covalent bonds for bio-passivation or bio-sensing applications. This approach to functionalizing Si wafers is in contrast to gold-thiol or siloxane chemistries and has been shown to lead to densely packed alkyl monolayers. In this study, a series of alkyl monolayers [CH₃(CH₂)_nCH=CH₂; n = 7, 9, 11, 13, 15] were directly covalent-linked to Si(1 1 1) wafers. The structures of these monolayers were studied using X-ray reflectometry (XRR) and AC impedance spectroscopy. Both techniques are sensitive to the variation in thickness with each addition of a CH₂ unit and thus provide a useful means for monitoring molecular-scale events. The combination of these techniques is able to probe not only the thickness, but also the interfacial roughness and capacitance of the layer at the immobilized surface with atomic resolution. Fundamental physical properties of these films such as chain canting angles were also determined.     

Holographic interferometry as electrochemical emission spectroscopy of a carbon steel in 5–20 ppm TROS C-70 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, as an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, as an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion tests, EI spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of TROS C-70 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical-emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which was obtained from the EI. spectroscopy. Consequently, holographic interferometry is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

XPS depth profiling study on the passive oxide film of carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties

X-ray photoelectron spectroscopy (XPS) was used to study the properties of passive oxide film that form on carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties. The thickness of the oxide films was determined to be approximately 4 nm and was not affected by the exposure time. Near the film/substrate interface the concentration of the Fe²⁺ oxides was higher than the concentration of the Fe³⁺ oxides; the layers near the free surface of the film mostly contained Fe³⁺ oxides. Chloride exposure decreased the thickness of the oxide films and changed their stoichiometry such that near the film/substrate interface Fe³⁺/Fe²⁺ ratio increased.     

Surface analysis of inhibitor films formed by imidazolines and amides on mild steel in an acidic environment

Imidazolines and amidic precursors were synthesized with good yields through an optimized process. These compounds were evaluated as corrosion inhibitors in an aqueous solution of 1.0 M HCl by gravimetric and polarization techniques. AISI 1018 carbon steel displayed a corrosion rate dependent on the molecular structure and concentration of inhibitor in the testing environment. Adsorption of inhibitors was found to follow the Langmuir's isotherm, this concept together with Gibbs’ free energy provided the basis to arrange corrosion inhibitors according to efficiency and stability. The surface analysis by AFM displayed that the damage on the metallic surface was considerably reduced in the presence of certain inhibitors. XPS determined the presence of a layer of inhibitor on the metal surface with protective properties.     

Inhibition of copper corrosion by bis-(1,1′-benzotriazoly)-α,ω-diamide compounds in aerated sulfuric acid solution

Three kinds of novel corrosion inhibitors, bis-(1,1′-benzotriazoly)-α,ω-succinyldiamide (BSU), bis-(1,1′-benzotriazoly)-α,ω-adipoyldiamide (BAD), and bis-(1,1′-benzotriazoly)-α,ω-azelayldiamide (BAZ) were synthesized and certified by IR and ¹H NMR. Their corrosion inhibition effects for copper in 0.5 M H₂SO₄ were evaluated by weight-loss method. It shows that among the three compounds, only BSU behaves better compared with BTA. The inhibition efficiency (IE) increased with increasing BSU concentration to 85.2% at the 5 × 10⁻⁴ M level. Polarization studies showed that BSU suppressed both anodic and cathodic corrosion reactions. The minimum energy conformation of these compounds was obtained by MM2 force field program. The two benzotriazoly moieties in BSU molecule are more parallel than in other compounds. This is benefit to increase the inhibition effects of BSU.     

In situ formation of low friction ceramic coatings on carbon steel by plasma electrolytic oxidation in two types of electrolytes

In situ formation of ceramic coatings on Q235 carbon steel was achieved by plasma electrolytic oxidation (PEO) in carbonate electrolyte and silicate electrolyte, respectively. The surface and cross-section morphology, phase and elemental composition of PEO coatings were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The bond strength of the coating was determined using a direct pull-off test. The hardness as well as tribological properties of the ceramic coating was primarily studied. The results indicated that the coating obtained in carbonate electrolyte was Fe₃O₄, while the coating achieved from silicate electrolyte was proved to be amorphous. Both kinds of coatings showed coarse and porous surface. The Fe₃O₄ coatings obtained in carbonate electrolyte showed a high bonding strength to the substrate up to 20 ± 2 MPa and the value was 15 ± 2 MPa for the amorphous coatings obtained in carbonate electrolyte. The micro hardness of the amorphous coating and the Fe₃O₄ coating was 1001 Hv and 1413 Hv, respectively, which was more than two and three times as that of the Q235 alloy substrate (415 Hv). The friction coefficient exhibited by amorphous coating and Fe₃O₄ coating was 0.13 and 0.11, respectively, both lower than the uncoated Q235 substrate which ranged from 0.17 to 0.35.     

Detection of the frustrated rotation mode of CO on Cu(0 0 1) by very low energy photoelectron spectroscopy

We have measured the very low energy photoelectron spectra of the clean and CO covered Cu(0 0 1) surfaces at low temperature (15 K). A step at 34.5 meV below the Fermi level appeared in the CO/Cu(0 0 1) spectra, while no structure was found at the same position in the clean Cu(0 0 1) spectrum. Furthermore, we have succeeded in measuring the spectral shift of the step to 33.2 meV below the Fermi level by isotopic substitution of the CO molecule. We have concluded that this step originates from the inelastic scattering of photoelectrons through excitation of the frustrated rotation mode of the CO molecule.     

Infrared reflection absorption study of carbon monoxide adsorption on Cu(1 0 0)-c(2 × 2)-Pd surfaces formed by palladium vacuum-depositions at various temperatures

Using infrared reflection absorption spectroscopy (IRRAS) and temperature programmed desorption (TPD), we investigated carbon monoxide (CO) adsorption and desorption behaviors on atomic checkerboard structures of Cu and Pd formed by Pd vacuum deposition at various temperatures of Cu(1 0 0). The 0.15-nm-thick Pd deposition onto a clean Cu(1 0 0) surface at room temperature (RT) showed a clear c(2 × 2) low-energy electron diffraction (LEED) pattern, i.e. Cu(1 0 0)-c(2 × 2)-Pd. The RT-CO exposure to the c(2 × 2) surfaces resulted in IRRAS absorption caused by CO adsorbed on the on-top sites of Pd. The LEED patterns of the Pd-deposited Cu(1 0 0) at higher substrate temperatures revealed less-contrasted c(2 × 2) patterns. The IRRAS intensities of the linearly bonded CO bands on 373-K-, 473-K-, and 673-K-deposited c(2 × 2) surfaces are, respectively, 25%, 22%, and 10% less intense than those on the RT-deposited surface, indicating that Pd coverages at the outermost c(2 × 2) surfaces decrease with increasing deposition temperature. In the initial stage of the 90-K-CO exposure to the RT surface, the band attributable to CO bonded to the Pd emerged at 2067 cm⁻¹ and shifted to higher frequencies with increasing CO exposure. At saturation coverage, the band was located at 2093 cm⁻¹. In contrast, two distinct bands around 2090 cm⁻¹ were apparent on the spectrum of the 473-K-deposited surface: the CO saturation spectrum was dominated by an apparent single absorption at 2090 cm⁻¹ for the 673-K-deposited surface. The TPD spectra of the surfaces showed peaks at around 200 and 300 K, which were ascribable respectively to Cu-CO and Pd-CO. Taking into account the TPD and IRRAS results, we discuss the adsorption-desorption behaviors of CO on the ordered checkerboard structures.     

Synergism between rare earth cerium(IV) ion and vanillin on the corrosion of steel in H2SO4 solution: Weight loss, electrochemical, UV-vis, FTIR, XPS, and AFM approaches

The synergism between rare earth cerium(IV) ion and vanillin (4-hydroxy-3-methoxy-benzaldehyde) on the corrosion of cold rolled steel (CRS) in 1.0 M H₂SO₄ solution at five temperatures ranging from 20 to 60 °C was first studied by weight loss and potentiodynamic polarization methods. The inhibited solutions were analyzed by ultraviolet and visible spectrophotometer (UV-vis). The adsorbed film of CRS surface containing optimum doses of the blends Ce⁴⁺-vanillin was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). The results revealed that vanillin had a moderate inhibitive effect, and the inhibition efficiency (IE) increased with the vanillin concentration. The adsorption of vanillin obeyed Temkin adsorption isotherm. Polarization curves showed that vanillin was a mixed-type inhibitor in sulfuric acid, while prominently inhibited the cathodic reaction. For the cerium(IV) ion, it had a negligible effect, and the maximum IE was only about 20%. However, incorporation of Ce⁴⁺ with vanillin improved significantly the inhibition performance. The IE for Ce⁴⁺ in combination with vanillin was higher than the summation of IE for single Ce⁴⁺ and single vanillin, which was synergism in nature. A high inhibition efficiency, 98% was obtained by a mixture of 25-200 mg l⁻¹ vanillin and 300-475 mg l⁻¹ Ce⁴⁺. UV-vis showed that the new complex of Ce⁴⁺-vanillin was formed in 1.0 M H₂SO₄ for Ce⁴⁺ combination with vanillin. Polarization studies showed that the complex of Ce⁴⁺-vanillin acted as a mixed-type inhibitor, which drastically inhibits both anodic and cathodic reactions. FTIR and XPS revealed that a protective film formed in the presence of both vanillin and Ce⁴⁺ was composed of cerium oxide and the complex of Ce⁴⁺-vanillin. The synergism between Ce⁴⁺ and vanillin could also be evidenced by AFM images. Depending on the results, the synergism mechanism was discussed from the viewpoint of adsorption theory.