Contributions to a More Realistic Characterization of Corrosion Processes on Cut Edges of Coated Metals Using Scanning Microelectrochemical Techniques, Illustrated by the Case of ZnAlMg-Galvanized Steel with Different Coating Densities.

Corrosion processes at cut edges of galvanized steels proceed as highly localized electrochemical reactions between the exposed bulk steel matrix and the protective thin metallic coating of a more electrochemically active material. Scanning microelectrochemical techniques can thus provide the spatially resolved information needed to assess the corrosion initiation and propagation phenomena, yet most methods scan cut edge sections as embedded in insulating resin to achieve a flat surface for scanning purposes. In this work, the galvanized coatings on both sides of the material were concomitantly exposed to simulated acid rain while characterizing the cut edge response using SECM and SVET techniques, thereby maintaining the coupled effects through the exposure of the whole system as rather realistic operation conditions. The cut edges were shown to strongly promote oxygen consumption and subsequent alkalization to pH 10-11 over the iron, while diffusion phenomena eventually yielded the complete depletion of oxygen and pH neutralization of the nearby electrolyte. In addition, the cathodic activation of the exposed iron was intensified with a thinner coating despite the lower presence of sacrificial anode, and preferential sites of the attack in the corners revealed highly localized acidification below pH 4, which sustained hydrogen evolution at spots of the steel-coating interface.

Durability of Reinforced Concrete with Additions of Natural Pozzolans of Volcanic Origin.

In this work, the properties of concrete modified with dosages of natural pozzolans (NP) in substitution of cement or superfine aggregates were evaluated. Proportions of 20/80 pozzolan/cement or pozzolan/superfine aggregates were selected for the additions of quarry and tuff pozzolans. Pozzolanic activity, durability, compressive strength, characteristic resistance, settling consistency, density, electrical resistivity, depth of water penetration, accessible porosity, and carbonation and chloride penetration were determined for the resulting concrete mixtures, and they were subsequently compared to the values obtained for the reference concrete batches without additions. The results of the cementitious mixtures supplemented with tuff (PZT) and quarry (PZQ) pozzolans, expressed in mmol/L, are consistent with the pozzolanism test, with [Ca(OH)2]/[OH-] ratios at 7 days are 6.03/60.19 for PZQ and 1.78/92.78 PZT. In addition to the pozzolanic activity at these dosages, the characteristic resistance and durability parameters required by EHE-08 were verified. Particular attention was given to the determination of the diffusion of chloride ions, introducing an instrumental modification of the accelerated integral method. The modification provides values of diffusion coefficients similar to those obtained by the other methods with the advantage of greater stability and quality of the measurement.

Contributions of Microelectrochemical Scanning Techniques for the Efficient Detection of Localized Corrosion Processes at the Cut Edges of Polymer-Coated Galvanized Steel.

Spatially resolved information on corrosion reactions operating at the cut edges of coated metals can be obtained using microelectrochemical scanning techniques using a suitable selection of operation modes and scanning probes. The scanning vibrating electrode technique (SVET) provides current density maps with a spatial resolution of the order of the dimensions of the sample, which allows the temporal evolution of the corrosion reactions to be followed over time. This leads to the identification and localization of cathodic and anodic sites, although the technique lacks chemical specificity for the unequivocal identification of the reactive species. The application of scanning electrochemical microscopy (SECM) was previously limited to image cathodic reaction sites, either due to oxygen consumption in the amperometric operation or by the alkalinisation of the electrolyte in potentiometric operation. However, it is shown that anodic sites can be effectively monitored using an ion-selective microelectrode (ISME) as a probe. The ISME probes detected differences in the local concentrations of Zn2+ and OH- ions from the cut edges of a complete coil coating system compared to the same system after the polymeric layers were removed. In this way, it has been shown that the inhibitor loading in the polymer layers effectively contributes to reducing the corrosion rates at the cut edge, thus helping to extend the useful life of the sacrificial galvanized layer bonded directly to the steel matrix. Additionally, these two probe configurations can be integrated into a multi-electrode tip for potentiometric operation to simultaneously monitor localized changes in pH values and metal ion dissolution in a single scan. Spatial and temporal distributions were further investigated using different rastering procedures, and the potential of constructing pseudomaps for 2D-imaging is described.

In Situ Investigation of the Cytotoxic and Interfacial Characteristics of Titanium When Galvanically Coupled with Magnesium Using Scanning Electrochemical Microscopy.

Recently, the cytotoxic properties of galvanically coupled Ti-Mg particles have been shown in different cells. This cytotoxic effect has been attributed mainly to Mg due to its tendency to undergo activation when coupled with Ti, forming a galvanic cell consisting of an anode (Mg) and a cathode (Ti). However, the role of the Ti cathode has been ignored in explaining the cytotoxic effect of Ti-Mg particles due to its high resistance to corrosion. In this work, the role of titanium (Ti) in the cytotoxic mechanism of galvanically coupled Ti-Mg particles was examined. A model galvanic cell (MGC) was prepared to simulate the Mg-Ti particles. The electrochemical reactivity of the Ti sample and the pH change in it due to galvanic coupling with Mg were investigated using scanning electrochemical microscopy (SECM). It was observed that the Ti surface changed from passive to electrochemically active when coupled with Mg. Furthermore, after only 15 min of galvanic coupling with Mg, the pH in the electrolyte volume adjacent to the Ti surface increased to an alkaline pH value. The effects of the galvanic coupling of Ti and Mg, as well as those of the alkaline pH environment, on the viability of Hs27 fibroblast cells were investigated. It was shown that the viability of Hs27 cells significantly diminished when Mg and Ti were galvanically coupled compared to when the two metals were electrically disconnected. Thus, although Ti usually exhibited high corrosion resistance when exposed to physiological environments, an electrochemically active surface was observed when galvanically coupled with Mg, and this surface may participate in electron transfer reactions with chemical species in the neighboring environment; this participation resulted in the increased pH values above its surface and enhanced generation of reactive oxygen species. These features contributed to the development of cytotoxic effects by galvanically coupled Ti-Mg particles.

Use of Amperometric and Potentiometric Probes in Scanning Electrochemical Microscopy for the Spatially-Resolved Monitoring of Severe Localized Corrosion Sites on Aluminum Alloy 2098-T351.

Amperometric and potentiometric probes were employed for the detection and characterization of reactive sites on the 2098-T351 Al-alloy (AA2098-T351) using scanning electrochemical microscopy (SECM). Firstly, the probe of concept was performed on a model Mg-Al galvanic pair system using SECM in the amperometric and potentiometric operation modes, in order to address the responsiveness of the probes for the characterization of this galvanic pair system. Next, these sensing probes were employed to characterize the 2098-T351 alloy surface immersed in a saline aqueous solution at ambient temperature. The distribution of reactive sites and the local pH changes associated with severe localized corrosion (SLC) on the alloy surface were imaged and subsequently studied. Higher hydrogen evolution, lower oxygen depletion and acidification occurred at the SLC sites developed on the 2098-T351 Al-alloy.

Spectroelectrochemical Behavior of Polycrystalline Gold Electrode Modified by Reverse Micelles.

The increasing demand for raising the reliability of electronic contacts has led to the development of methods that protect metal surfaces against atmospheric corrosion agents. This severe problem implies an important economic cost annually but small amounts of corrosion inhibitors can control, decrease or avoid reactions between a metal and its environment. In this regard, surfactant inhibitors have displayed many advantages such as low price, easy fabrication, low toxicity and high inhibition efficiency. For this reason, in this article, the spectroelectrochemical behavior of polycrystalline gold electrode modified by reverse micelles (water/polyethyleneglycol-dodecylether (BRIJ 30)/n-heptane) is investigated by atomic force microscopy (AFM), potentiodynamic methods and electrochemical impedance spectroscopy (EIS). Main results indicate a strong adsorption of a monolayer of micelles on the gold substrate in which electron tunneling conduction is still possible. Therefore, this method of increasing the corrosion resistance of gold contacts is usable only in conditions of long-term storage but not in the operation of devices with such contacts. In this regard, the micelle coating must be removed from the surface of the gold contacts before use. Finally, the aim of the present work is to understand the reactions occurring at the surfactant/metal interface, which may help to improve the fabrication of novel electrodes.

Evaluation of in vitro corrosion resistance and in vivo osseointegration properties of a FeMnSiCa alloy as potential degradable implant biomaterial.

In vitro electrochemical characterization and in vivo implantation in an animal model were employed to evaluate the degradation behaviour and the biological activity of FeMnSi and FeMnSiCa alloys obtained using UltraCast (Ar atmosphere) melting. Electrochemical characterization was based on open circuit potential measurement, electrochemical impedance spectroscopy and potentiodynamic polarization techniques while the alloys were immersed in Ringer's solution at 37 °C for 7 days. Higher corrosion rates were measured for the Ca-containing material, resulting from inefficient passivation of the metal surface by oxy-hydroxide products. In vivo osseointegration was investigated on a tibia implant model in rabbits by referring to a standard control (AISI 316 L) stainless steel using standard biochemical, histological and radiological methods of investigation. Changes in the biochemical parameters were related to the main stages of the bone defect repair, whereas implantation of the alloys in rabbit's tibia provided the necessary mechanical support to the injured bone area and facilitated the growth of the newly connective tissue, as well as osteoid formation and mineralization, as revealed by either histological sections or computed tomography reconstructed images and validated by the bone morphometric indices. The present study highlighted that the FeMnSiCa alloy promotes better osteoinduction and osseconduction processes when compared to the base FeMnSi alloy or with AISI 316 L, and in vivo degradation rates correlate well with corrosion resistance measurements in Ringer's solution.

Kinetic Passivation Effect of Localized Differential Aeration on Brass.

Invited for this month's cover are collaborators from Ruhr University Bochum (Germany), Technical University Munich (Germany), and University of La Laguna, Tenerife (Spain). The cover picture shows the passivation effect of a liquid in a brass tube in the presence of oxygen in the gas phase. Read the full text of the article at 10.1002/cplu.201500398.

Kinetic Passivation Effect of Localized Differential Aeration on Brass.

The formation of a localized differential aeration cell on metals, susceptible to both anodic and cathodic corrosion, is a serious threat because of multiple degradation processes commencing with the passivation layer destruction. By using local electrochemical and X-ray dispersive techniques, it has been demonstrated that the differential aeration cell formed on high brass (α-brass, Cu65-Zn35) in the presence of 1H-benzotriazole or 5-methyl-1H-benzotriazole plays both corrosion-inhibiting and accelerating roles, depending on the inhibitor exposure time. Alternating-current scanning electrochemical microscopy was used to image local electrochemical activity, whereas energy-dispersive X-ray spectroscopy provided evidence for the mechanism of the observed phenomena. Short-term exposure to the inhibitor (5 min) promotes the formation of a passivation layer in the waterline region. In contrast, after prolonged exposure (45 min), a deficient passivation layer develops for both inhibitors. An excess of zinc(II)-inhibitor complexes in the passivation layer is accountable for the corrosion resistance of the region with high differential aeration. Rapid dezincification and local alkalinization facilitate the initial rapid formation of a passivation layer in the area under differential aeration to preserve its composition upon further modification.

In situ scanning electrochemical microscopy (SECM) detection of metal dissolution during zinc corrosion by means of mercury sphere-cap microelectrode tips.

This work presents a scanning electrochemical microscopy (SECM)-based in situ corrosion probing methodology that is capable of monitoring the release of zinc species in corrosion processes. It is based on the use of Hg-coated Pt microelectrodes as SECM tips, which offer a wider negative potential range than bare platinum or other noble-metal tips. This allows for the reduction of zinc ions at the tip to be investigated with low interference from hydrogen evolution and oxygen reduction from aqueous solutions. The processes involved in the corrosion of zinc during its immersion in chloride-containing solutions were successfully monitored by scanning the SECM tip, set at an adequate potential, across the sample either in one direction or in the X-Y plane parallel to its surface. In this way, it was possible to detect the anodic and cathodic sites at which the dissolution of zinc and the reduction of oxygen occurred, respectively. Additionally, cyclic voltammetry (CV) or constant potential measurements were used to monitor the release of zinc species collected at the tip during an SECM scan.

Application of AC-SECM in corrosion science: local visualisation of inhibitor films on active metals for corrosion protection.

The suitability of frequency-dependent alternating-current scanning electrochemical microscopy (4D AC-SECM) for investigation of thin passivating layers covering the surface of corrosion-inhibited metals has been demonstrated. Inhibition of copper corrosion by benzotriazole (BTAH) and methylbenzotriazole (MBTAH), which are effective inhibitors for this metal under many environmental conditions, was investigated. Strong dependencies were found for the AC z-approach curves with both the duration of the inhibitor treatment and the frequency of the AC excitation signal applied in AC-SECM. Both negative and positive feedback behaviours were observed in the AC approach curves for untreated copper and for Cu/BTAH and Cu/MBTAH samples. Negative feedback behaviour occurred in the low-frequency range, whereas a positive feedback effect was observed at higher frequencies. A threshold frequency related to the passage from negative to positive regimes could be determined in each case. The threshold frequency for inhibitor-modified samples was found always to be significantly higher than for the untreated metal, because the inhibitor film provides electrical insulation for the surface. Moreover, the threshold frequency increased with increasing surface coverage by the inhibitor. 4D AC-SECM was successfully applied to visualizing spatially resolved differences in local electrochemical activity between inhibitor-free and inhibitor-covered areas of the sample.

Revealing structural effects, part II: the influence of molecular structure on the adsorption of butanol isomers on platinum.

The nature of the adsorbates formed when butanol isomers interact with platinum electrodes in a perchloric acid medium was investigated by the application of on-line differential electrochemical mass spectrometry (DEMS) and cyclic voltammetry. In this way, the reactivity of the residues remaining on the electrode surface after a flow-cell experiment was established for the different molecules. It was found that the four isomers form strongly adsorbed species on the electrode, which undergo both electro-oxidation and electroreduction, depending on the potential applied at the electrode. Oxidative stripping of the adsorbates produces CO2 as the only oxidation product, whereas propane and the corresponding butane isomer are obtained on platinum in the hydrogen adsorption potential region. The yields of these hydrocarbons were found to depend strongly on the nature of the butanol isomer and on the adsorption potential. According to these results, it can be concluded that fragmentation of the butanol isomers occurs during adsorption and reduction reactions. C4 alkene and acetyl species are proposed as the adsorbed intermediates in all cases.

Characterization of the catalytic films formed on stainless steel anodes employed for the electrochemical treatment of cuprocyanide wastewaters.

Surface composition changes at stainless steel anodes in an electrochemical reactor applied for the electrochemical treatment of cuprocyanide-containing wastewaters operating under different hydrodynamic conditions were investigated. Under highly alkaline conditions in situ generation of a surface film on the anode with catalytic properties towards cyanide electrolysis was observed. X-ray photoelectron spectroscopy (XPS) results demonstrated that only copper oxi-hydroxide compounds constitute the surface film developed on the stainless steel anodes, as no traces of N- and C-containing compounds were observed. The collected XPS spectra revealed relevant details concerning the oxidation states of copper in the film, and the products Cu2O, CuO and Cu(OH)2 were identified on the surface of the anodes. However, the quantitative proportions of the individual products differ and depend on the type of mixing employed during reactor operation.

Electrochemical behavior of different preparations of plasma-sprayed hydroxyapatite coatings on Ti6Al4V substrate.

The corrosion behavior of four different preparations of plasma-sprayed hydroxyapatite (HA) coatings on Ti6Al4V substrates in static Hank's balanced salt solution was investigated using dc potentiodynamic and ac impedance techniques. Two different nominal thicknesses, 50 microm and 200 microm, and two different spraying conditions, were considered. The electrochemical impedance experiments proved this technique to be very suitable for the investigation of the electrochemical behavior of surgical implant alloys when they are coated with HA, which is characterized by the dissolution and passivation characteristics of the underlying metal substrate. Because the coatings are porous, ionic paths between the electrolytic medium and the base material can eventually be produced, resulting in the corrosion of the coated metal. Differences in the corrosion resistance of the coated materials were detected, and a relevant model for the description of the coating degradation in the biosimulating solution was proposed. The model consisted of the description of the coated system in terms of a two-layer model of the surface film. Significant differences in electrochemical behavior for similar nominal thicknesses of HA coatings obtained under different spraying conditions were found.

Degradation characteristics of hydroxyapatite coatings on orthopaedic TiAlV in simulated physiological media investigated by electrochemical impedance spectroscopy.

This paper concentrates on the degradation characteristics of hydroxyapatite (HA) coatings on orthopaedic Ti-6Al-4V alloy while immersed in Ringer's salt solution, which were investigated by electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy measurements were used to in situ characterize the electrochemical behavior of the passivated alloy covered with HA during aging in Ringer's solution. Comparison of the electrochemical data for the coated material with that for the uncoated metal substrate was also performed. The characteristic feature that describes the electrochemical behavior of the coated material is the coexistence of large areas of the coating itself with pores where the substrate is exposed to the aggressive media. The interpretation of results was thus performed in terms of a two-layer model of the film, in which the precipitation of hydrated oxide or phosphate compounds seals the pores left by the ceramic coating. The blocking effect due to salt precipitation inside the pores produces an enhancement of the resistance values, thus effectively diminishing the metal ion release in the system.

Revealing structural effects: electrochemical reactions of butanols on platinum.

Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state.