Conducting polyaniline (Pani) was prepared in the presence of methane sulfonic acid (MeSA) as dopant by chemical oxidative polymerization. The Pani–MeSA polymer was characterized by FT-IR, UV–vis, X-ray diffraction (XRD) and impedance spectroscopy. The polymer was dispersed in polyvinylacetate and coated on carbon steel samples by a dipping method. The electrochemical behavior and anticorrosion properties of the coating on carbon steel in 3% NaCl were investigated using open-circuit potential (OCP) versus time of exposure, and electrochemical techniques including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and cyclic voltammetry (CV). During initial exposure, the OCP dropped about 0.35 V and the interfacial resistance increased several times, indicating a certain reduction of the polymer and oxidation of the steel surface. Later the OCP shifted to the noble direction and remained at a stable value during the exposure up to 60 days. The EIS monitoring also revealed the initial change and later stabilization of the coating. The stable high OCP and low coating impedance suggest that the conducting polymer maintains its oxidative state and provides corrosion protection for carbon steel throughout the investigated period. The polarization curves and CV show that the conducting polymer coating induces a passive-like behavior and greatly reduces the corrosion of carbon steel.

Corrosion of iron exposed to H2S saturated solution at pH 4 was studied by electrochemical impedance spectroscopy, weight loss coupons and surface analysis. Hydrogen permeation was also used as indirect means of evaluating the intensity of the proton reduction reaction leading to hydrogen entry into the metal. Since corrosion in this type of test solution results in the rapid build-up of a conductive and highly porous iron sulfide scale, a specific contribution of the film has to be considered. An impedance model was thus proposed. The faradaic anodic impedance consists of a two-step reaction with charge transfer and adsorption – desorption. An additional contribution, associated with the conductive and highly porous iron sulfide film was added in parallel. This contribution, mostly visible in the low frequency domain, presents a 45° tail associated with a porous electrode behavior. This model was well adapted to describe impedance diagrams measured at various exposure times, up to 620 h. Charge transfer resistance determined from impedance analysis allowed calculating the evolution with time of the corrosion current density. A very good correlation was found between this corrosion current density and the hydrogen permeation current density. As expected in our experimental conditions, a permeation efficiency close to 100% is demonstrated. Corrosion rate of 490 μm/year was measured by weight-loss specimens, confirming the validity of the impedance analysis, which resulted in a calculated corrosion rate of 530 μm/year.

The acid pickling of Al-3at.%Mg, Al-3at.%Cu, and aluminum alloy (AA) 7449-T651 in nitro-sulfuro-ferric acid was investigated using element-resolved electrochemistry (AESEC) in terms of their elemental dissolution kinetics. The influence of this acid pickling on the subsequent Zr-based conversion coating process was also demonstrated on these alloys by monitoring the dissolution rates of the alloying elements during conversion and the final elemental depth profiles from calibrated glow discharge-optical emission spectroscopy (GD-OES). The separate influence of fluoride (F−) and nitrate (NO3−) as additives on the dissolution kinetics was also investigated when added to the conversion coating bath solution. F− increased the dissolution rate of Al but no significant effect was seen on Cu, while NO3− enhanced the dissolution rates of both elements. Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS) data suggested a greater Zr-fluoride presence if the conversion coating was performed on a non-acid-pickled surface. 

The paper aims to provide some insight into the fundamental mechanisms for the behavior of cerium oxides nanoparticles as corrosion inhibitors for steel. The work was carried out on mild steel water based dispersions of cerium oxides nanoparticles in presence of both, sulfates and chlorides. Ceria nanoparticles were produced via precipitation of cerium Ce(NO3)3.6H 2O in water, particles of about 70 nm hydrodynamic diameter were obtained. The analysis of the effectiveness of the ceria nanoparticles as corrosion inhibitors was performed by means of electrochemicaltechniques such as electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) versus time measurements. The experimental measurements suggested that cerium oxide affects the electrochemical properties of mild steel surface; they promoted an ennoblement effect and strong modifications in the impedance response.

The pit propagation behavior of copper (UNS C11000) was investigated from an electrochemical perspective using the artificial pit method. Pit growth was studied systematically in a range of HCO 3 -, SO 4 2- and Cl - containing-waters at various concentrations. Pit propagation was mediated by the nature of the corrosion products formed both inside and over the pit mouth (i.e., cap). Certain water chemistry concentrations such as those high in sulfate were found to promote fast pitting that could be sustained over long times at a fixed applied potential but gradually stifled in all but the lowest concentration solutions. In contrast, Cl - containing waters without sulfate ions resulted in slower pit growth and eventual repassivation. These observations were interpreted through understanding of the identity, amount and porosity of corrosion products formed inside and over pits. These factors controlled their resistive nature as characterized using electrochemical impedance spectroscopy. A finite element model (FEM) was developed which included copper oxidation kinetics, transport by migration and diffusion, Cu(I) and Cu(II) solid corrosion product formation and porosity governed by equilibrium thermodynamics and a saturation index, as well as pit current and depth of penetration. The findings of the modeling were in good agreement with artificial pit experiments. Malachite, bronchantite, cuprite, nantokite and atacamite corrosion products were both observed in experiment and predicted by the model. Stifling and/or repassivation occurred when the resistance of the corrosion product layer became high enough to lower the pit bottom potential and pit current density such as 10 -5 A/cm 2 could be attained with thick and dense layer. The ramifications of these findings towards pit propagation characteristics in potable waters will be discussed with improved insight into the roles of Cl - and SO 4 2- ions. © 2011 Elsevier Ltd. All Rights Reserved.

We report on a small and simple graphene-based potentiometric sensor for the measurement of intracellular glucose concentration. A fine borosilicate glass capillary coated with graphene and subsequently immobilized with glucose oxidase (GOD) enzyme is inserted into the intracellular environment of a single human cell. The functional groups on the edge plane of graphene assist the attachment with the free amine terminals of GOD enzyme, resulting in a better immobilization. The sensor exhibits a glucose-dependent electrochemical potential against an Ag/AgCl reference microelectrode which is linear across the whole concentration range of interest (10 - 1000 μM). Glucose concentration in human fat cell measured by our graphene-based sensor is in good agreement with nuclear magnetic resonance (NMR) spectroscopy. 

Most metal nanoparticles (NPs), except noble metal NPs, rapidly form a thin surface oxide in ambient conditions. The protective properties of these oxides improve or worsen depending on the environment, e.g., the human lung. Several properties, including the chemical/electrochemical stability and defect density, determine the capacity of these surface oxides to hinder the bulk metal from further oxidation (corrosion). The aim of this study was to investigate whether electrochemical surface oxide characterization of non-functionalized base metal NPs of different characteristics (Al, Mn and Cu) can assist in understanding their bioaccessibility (metal release) in cell media (DMEM+) and their cytotoxic properties following exposure in lung epithelial (A549) cells. The composition and valence states of surface oxides of metal NPs and their electrochemical activity were investigated using an electrochemical technique based on a graphite paste electrode to perform cyclic voltammetry in buffer solutions and open circuit potential measurements in DMEM+. The electrochemical surface oxide characterization was complemented and verified by Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The open circuit potential trends in DMEM+ correlated well with metal release results in the same solution, and provided information on the kinetics of oxide dissolution in the case of Cu NPs. Extensive particle agglomeration in cell medium (DMEM+) was observed by means of photon-cross correlation spectroscopy for all metal NPs, with sedimentation taking place very quickly. As a consequence, measurements of the real dose of added non-functionalized metal NPs to cell cultures for cytotoxicity testing from a sonicated stock solution were shown necessary. The cytotoxic response was found to be strongly correlated to changes in physico-chemical and electrochemical properties of the surface oxides of the metal NPs, the most potent being Cu NPs, followed by Mn NPs. No cytotoxicity was observed for Al NPs. The electrochemical surface oxide characterization corresponded well with other tools commonly used for nanotoxicological characterization and provided additional information.

Steels with high mechanical performance are prone to hydrogen embrittlement and environmental assisted cracking. Under atmospheric corrosion conditions, the source of hydrogen can be the steel corrosion process itself or galvanic coupling with a metallic coating. Electrochemical behaviour of Press Hardened Steel (PHS) under electrolyte films of different thicknesses using local electrochemical techniques was studied on a fundamental level. Scanning Vibrated Electrode Technique (SVET) was applied to study the evolution and localization of the corrosion process during PHS immersion in NaCl electrolyte. Kelvin Probe (KP) was used as a reference electrode to obtain cathodic and anodic polarization curves on PHS surfaces which were covered by thin electrolyte films (60 to 500 µm) of 0.1 M NaOH and 0.6 M NaCl. For both electrolytes, a strong increase in the oxygen reduction rate due to the decreasing of electrolyte thickness has been clearly demonstrated. Data are correlated well with a theoretical plot determined by Nernst-Fick equation. The influence of the rust layers on the kinetics of corrosion reactions under thin electrolyte films was investigated using KP. © 2023

The micro-galvanic interactions between Cu-Fe-Mn-Li-containing aluminides and the alloy matrix of aluminium alloy AA2099 during chloride-induced corrosion were investigated in-situ with real-time monitoring of the local contact potential difference (VCPD) using the scanning Kelvin probe force microscopy (SKPFM) at controlled relative humidities. The aluminides showed noble potentials and were able to ennoble their neighbouring matrix sites when a cluster of aluminides surrounded the matrix. The matrix, hence, adopted a more positive VCPD, towards that of the aluminides. The anode-to-cathode ratio changed throughout the corrosion exposure and was seen to show a dynamic character. Much higher local VCPD activities were recorded during the earliest stages of corrosion, when the Al-Li AA2099 surface was first exposed to high humidities, than in later RH cycles; a phenomenon not seen in other aluminium alloys.

Electrochemical impedance spectroscopy (EIS) and Scanning Kelvin probe (SKP) were applied to study the zinc/polymer interface. The coating capacitance and the drop of potential across the zinc/epoxy interface are investigated as a function of water penetration and hydrolysis of adhesion bonds. Water penetrates to the interface, decreasing thus the potential drop and increasing the capacitance. Further removal of water leads to the restoration of bonds accompanied by a decrease in capacitance and the return to the initial potential distribution across the interface. Commercial high-performance coil coatings applied to galvanized steel were studied in order to correlate the interface stability and the tendency to blistering. EIS and SKP measurements allowed the evaluation of the electrochemical conditions at the interface. Local adhesion failures caused non-uniformity in the potential profile measured by SKP. Monitoring of changes in impedance at low frequency related to the interface during temperature cycling may be useful for the evaluation of the tendency to blistering.

The surface reactivity and the elemental dissolution of a high-strength aerospace alloy (AA7449-T651) during acid pickling was investigated with element-resolved electrochemistry (AESEC). The results demonstrated a sequential dissolution of Mg, Al, Zn and Cu, following the order of their respective galvanic reactivity in common acid pickling solutions. The enrichment of Cu during pickling with the H2SO4 solution was observed. The effect of oxidizing solution components HNO3 and Fe(III) on Cu dissolution were investigated using an experimental Evans diagram approach. 

Acid pickling is a one-step process prior to the conversion coating of aluminum alloys, an alternative to the two-step degreasing-deoxidizing. Selective dissolution may lead to enrichment or depletion of alloying elements with important consequences for corrosion resistance. In this work, the mechanisms of selective dissolution were explored using element-resolved electrochemistry for Al-3at.%Cu and Al-3at.%Mg, representing two extremes of the galvanic series. Pickling reactions were investigated in sulfuric and nitric acids with and without Fe(III) additives. The microstructure of the Al-3at.%Cu alloy was varied by heat treatment. Al-3at.%Mg showed congruent dissolution throughout the steady state in all electrolytes while Al-3at.%Cu underwent selective dissolution with surface enrichment of Cu and a significant release of detached Cu-rich particles in sulfuric acid. With the presence of Fe(III) in the electrolyte, Cu dissolved congruently, and the dissolution kinetics of these two alloys were also markedly enhanced. Experimental Evans diagrams were determined to clarify the electrochemical nature of the reactions. © 2023 The Author(s)

Corrosion and stress-corrosion related failures often compromise the integrity of critical metallic components during their service, raising significant concerns. It is crucial to comprehend the crack initiation mechanism and the impact of alloy microstructure on this crack initiation process. It is known that the introduction of unique microstructures through metal additive manufacturing brings new challenges. This study aims to investigate, for the first time, the effects of microstructural alterations resulting from fluctuations in laser power during laser powder bed fusion on the surface cracking initiation mechanism and electrochemical behaviour of Ni-Fe-Cr alloy 718, which is widely used in applications that require exceptional strength and corrosion resistance. To carry out this investigation, microcapillary electrochemical methods were combined with high-resolution techniques (TEM, SEM, AFM). The findings emphasize the existence of an optimal range of process parameters that effectively mitigate corrosion and crack initiation susceptibility. This work demonstrated that slight deviations in laser power from this optimal value result in diverse alterations at the micro and submicron scales. These alterations include increased subgrain width, porosity, dislocation density, density of nanovoids, and distribution of carbides. Importantly, these changes, particularly in dislocation and nanovoid densities caused by minor variations in process parameters, significantly affect the material's susceptibility to corrosion initiation and stress-assisted surface cracking. 

Adsorption of mussel adhesive protein (Mefp-1) derived from the marine mussel Mytilus edulis and its corrosion inhibition for carbon steel were studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements in NaCl solutions at 01 4.6. The results indicate that the Mefp-1 confers significant corrosion inhibition of carbon steel, and the chloride concentration of the solution has an influence on the inhibition efficiency. Within a short exposure time, the inhibition efficiency is higher in the solution with a higher chloride concentration, whereas, for longer exposure time, up to one week, higher inhibition efficiency was obtained in the solution with a lower chloride concentration. AFM imaging was used both ex situ and in situ to investigate Mefp-1 adsorption. The in situ AFM measurements enable the protein adsorption on carbon steel to be visualized in real time in the solution. The AFM images illustrate how the Mefp-1 layer is formed on carbon steel. Measurements using bovine serum albumin (BSA) were also performed for comparison. The results showed that BSA also confers significant corrosion inhibition of carbon steel even though the BSA film formation process is slightly different from that of Mefp-1.

Thin films composed of Mefp-1 and ceria nanoparticles have shown an increasing corrosion inhibitioneffect with time for carbon steel in acidic aqueous solutions containing phosphate, which motivates adetailed study of the inhibition mechanism by in situ confocal Raman micro-spectroscopy (CRM) andelectrochemical impedance spectroscopy (EIS) measurements. The presence of both CeO2and ferricoxides in the thin composite film was demonstrated by X-ray photoelectron spectroscopy analysis. TheRaman spectra assisted by DFT calculations suggest that Mefp-1 forms tri-Fe3+/Mefp-1 complexes andbinds to ceria nanoparticles in the composite film. The in situ CRM measurement allow us to followthe development of corrosion products. The measurements show a mixture of Fe oxides/oxyhydroxides,and also indicate that ferrous oxides may be further oxidized by the composite film. Moreover, phos-phate ions react with the Fe ions released from the surface to form iron-phosphate deposits, whichbecome incorporated into the corrosion product layer and the composite film. The EIS measurementssuggest a layered surface structure formed by the initial Mefp-1/ceria composite layer and the corrosionproducts/iron-phosphate deposits. These measurements also demonstrate the greatly increased inhibi-tion effect of the composite film in the presence of the phosphate ions. The consistent CRM and EIS resultssuggest that the iron-phosphate deposits heal defects in the composite film and corrosion product layer,which results in a significantly improved corrosion inhibition of the Mefp-1/ceria composite film duringinitial and long term exposure.