Sweet aqueous solution for electrochemical synthesis of polypyrrole: Part 1-A. On non-ferrous metals

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminum electrode in aqueous medium of 0.1 M saccharin sodium salt and 0.5 M pyrrole. Scanning electron microscopy shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. Moreover, energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) reveal a good homogeneity of the film achieved in cyclic voltammetry during 10 cycles. The electrochemical impedance spectroscopy (EIS) results show that the coating decreases the polarization resistance of the aluminum electrode. The open circuit potential (OCP) and dc polarization measurements achieved in HCl and NaCl solutions displayed a large positive displacement of corrosion potential and a reduction of corrosion current in the case of PPy coating electrode in comparison with electrode bare.     

Sweet aqueous solution for electrochemical synthesis of polypyrrole part 1B: On copper and its alloys

The electrochemical synthesis of polypyrrole (PPy) on copper and brass has been successfully achieved in sodium saccharinate and pyrrole aqueous medium. The synthesized coating under several electrochemical techniques such as cyclic voltammetry, galvanostatic and potentiostatic is homogeneous and adherent. PPy has been characterized by SEM, XPS, IR and Raman spectroscopy and its quality has been confirmed. The doping level obtained from N 1s XPS signal of the oxidized PPy depends on the electrochemical technique used to produce the film. The corrosion performance of PPy/copper and PPy/brass has been evaluated in 3% NaCl and 0.1 M HCl using linear polarization and electrochemical impedance spectroscopy. The results show that PPy coating electrodeposited from sodium saccharinate exhibits significant corrosion protection properties.     

Pyrrole nanoscaled electropolymerization: Effect of the proton

Polypyrrole (Ppy) nanowires are electrochemically synthesized using the nanochannels of a proton-modified natural zeolite clinoptilolite (HNZ). The synthetic inorganic structures Y zeolite and clay montmorillonite (M) in acid form (HY and HM) are also employed for pyrrole polymerization. The generation of Ppy with electrochemical activity is favored in a strongly acidic nanoscaled environment, in comparison with the polymer synthesized in the hosts without previous proton modification. It is proposed that the reduction/oxidation responses are a consequence of the polymer protonation/deprotonation where the H⁺ ions possibly act as charge transfer promoters. The well defined redox signals of Ppy included in HNZ, compared to the HY and HM, suggest that the polymeric units are held more tightly to the channels walls due to its complex framework. The TEM image of HNZ-Ppy reveals the presence of the polymer nanowires inside the natural zeolite framework. It is also found that the one electron oxidation process do not depend on first order monomer concentration but lower (0.38) for Ppy growth in HNZ, which is related to the spatial restriction of the host.     

Chromate leaching from inhibited primers: Part I. Characterisation of leaching

Leaching and characterisation studies have been undertaken on two chromate-inhibited epoxy polyamide primers. Leaching was carried out in 5% (w/v) NaCl solutions at different pH values (1, 3, 5 and 7) and the amount of Cr released into solution was monitored over time. Cr release was initially high, but as the immersion time increased the leaching from the primers slowed. Prior to and after immersion, the primers were characterised by a number of techniques including electron microprobe analysis, X-ray microdiffraction, Raman spectroscopy, and positron annihilation lifetime spectroscopy. The unexposed primers were found to contain the inorganic phases SrCrO₄, BaSO₄ and TiO₂ (anatase or rutile). Upon immersion, water uptake by the primers was observed, together with a decrease in the amount of SrCrO₄ in the primers. These studies provide insights into the mechanism of chromate leaching from inhibited primers.     

Single pit on iron generated by SECM: An electrochemical impedance spectroscopy investigation

The analysis of a single pit behavior on iron in various media (sulfuric acid, borate buffer, and potassium hydroxide solutions) is reported. The use of SECM technique to generate a single pit has allowed usual electrochemical techniques to be applied. Electrochemical impedance spectroscopy was used to characterize the pit propagation. In acidic solution, the pit returned to its passive state quickly whereas for the same amount for chloride ions generated locally, the pits remained active for long time in KOH solution. An intermediate behavior was evidenced in borate buffer for which a slow repassivation ascribed to the accumulation of insoluble corrosion products inside the pit was observed. The Raman analysis also evidenced the strong influence of the thin-layer-cell configuration on the nature of corrosion products in borate buffer.     

Alkali sorption by C-S-H and C-A-S-H gels: Part II. Role of alumina

In Part I, it was shown that alkali partition between C-S-H gel and an aqueous phase can be represented by a partition function, R_d, the numerical value of which, at constant temperature, is defined by the Ca/Si ratio. This R_d value is constant or nearly so over wide ranges of NaOH and KOH concentrations up to ∼0.3 M. In the present paper, Al has been introduced to form C-A-S-H gels, and the influence of Al on alkali sorption properties was determined: Approximately 6-7% replacement of Si by Al was used. Microprobe evidence is presented to show that the Al is actually in solid solution. Introduction of Al into C-S-H markedly increases R_d, indicating enhancement of alkali binding. The results underpin and quantify the beneficial effects of alkali binding arising from the introduction of aluminous supplementary cementing materials, such as fly ash, into cement pastes.     

Potassium sorbate—A new aqueous copper corrosion inhibitor: Electrochemical and spectroscopic studies

This work presents the novel nature of 2,4-hexadienoic acid potassium salt (potassium sorbate (KCH₃CHCHCHCHCO₂)) as an effective copper aqueous corrosion inhibitor. The influence of pH and potassium sorbate concentration on copper corrosion in aerated sulfate and chloride solutions is reported. Degree of copper protection was found to increase with an increase in potassium sorbate concentration; an optimum concentration of this inhibitor in sulfate solutions was found to be 10 g/L. Copper is highly resistant to corrosion attacks by chloride ions in the presence of potassium sorbate. X-ray photoelectron spectroscopy (XPS) studies suggest that copper protection is achieved via the formation of a mixed layer of cuprous oxide, cupric hydroxide and copper(II)-sorbate at the metal surface.     

Understanding aluminum behaviour in aqueous alkaline solution using coupled techniques: Part I. Rotating ring-disk study

Rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements have been undertaken to study the behaviour of pure aluminum electrodes in alkaline media. The measurements did consist of linear sweep voltammetry from anodic to cathodic potentials on 4N, 5N or 5N5-aluminum samples in 4 M aqueous potassium hydroxide solution. In the potential range studied (−0.7 V versus NHE to −2.5 V versus NHE) the aluminum undergoes oxidation/dissolution into aluminates anions at high electrode potential while it yields strong hydrogen evolution at low potentials. Thanks to the RRDE technique, we show that hydrogen starts to evolve from the aluminum electrode even above the open circuit potential. Also, the oxidation state of superficial aluminum varies according to the electrode potential: whereas non-conducting aluminum oxides are present above the open-circuit potential hindering hydrogen evolution reaction (HER), they tend to disappear below the ocp, due to the strong hydrogen evolution, following the probable porous oxide layer blow up induced by the hydrogen bubbles formation. In consequence at very low potential, HER occurs on bare aluminum, HER kinetics being much faster than on oxide-covered aluminum.     

Inhibition of mild steel corrosion in hydrochloric acid solution by triazole derivatives: Part I. Polarization and EIS studies

A comparative study of 5-amino-1,2,4-triazole (5-ATA), 5-amino-3-mercapto-1,2,4-triazole (5-AMT), 5-amino-3-methylthio-1,2,4-triazole (5-AMeTT) and 1-amino-3-methylthio-1,2,4-triazole (1-AMeTT) as inhibitors for mild steel corrosion in 0.1 M HCl solution at 20 °C was carried out. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were applied to study the metal corrosion behaviour in the absence and presence of different concentrations of these inhibitors under the influence of various experimental conditions. Measurements of open circuit potential (OCP) as a function of time till reaching the steady-state potentials (E_st) were also established. The studies have shown that 5-AMT was the most efficient inhibitor reaching values of inhibition efficiency (IE%) up to 96% at a concentration of 10⁻³ M. Polarization curves showed that the four studied compounds act as mixed inhibitors. The potential of zero charge (PZC) of mild steel was determined in 0.1 M HCl in the absence and presence of the studied inhibitors. The effect of chemical structure of the four tested inhibitors was discussed. Results obtained from OCP versus time, polarization and impedance measurements are in good agreement.     

Pyrrole-based silane primer for corrosion protection of commercial Al alloys: Part I: Synthesis and spectroscopic characterization

Chromate-free, direct-to-metal treatment using a pyrrole-based silane (PySi) was developed for protection against corrosion of as-received commercial wrought Al alloys of the series 1xxx, 2xxx, 5xxx and 6xxx. The metal surface was modified following the simple procedure for silane deposition by immersion in PySi hydrolyzed solution and curing. The spectroscopic characterization indicates that crosslinked composite PPySi network, containing both polysiloxane and polypyrrole units due to co-polymerization of PySi molecules, is produced by self-assembling of PySi soluble macro-oligomers onto the metallic substrates upon adsorption, with three-dimensional crosslink during heat treatment. Highly ordered well-packed and adherent PPySi film of the order of microns is obtained by just one immersion step in PySi primer. Control coatings of polymethylsiloxane (PMeSi) and polypyrrole (Ppy), the latter synthesized electrochemically, were investigated in parallel.     

Influence of anode material on the electrochemical oxidation of 2-naphthol: Part 2. Bulk electrolysis experiments

The electrochemical oxidation of 2-naphthol has been studied by galvanostatic electrolysis, using a range of electrode materials such as lead dioxide, boron-doped diamond (BDD) and Ti-Ru-Sn ternary oxide anodes. The influence of some operating parameters, such as current density, flow-rate and chloride concentration on naphthol oxidation has been investigated in order to find the optimum experimental conditions. Measurements of chemical oxygen demand, HPLC and total organic carbon have been used to follow the oxidation. The experimental data indicate that on PbO₂ and BDD, naphthol oxidation takes place by reaction with electrogenerated hydroxyl radicals and is favoured by low current density and high flow-rate. On the contrary, on a Ti-Ru-Sn ternary oxide the mineralisation of naphthol occurs only in the presence of chloride ions that act as redox mediators and COD removal is affected by chloride concentration and is not significantly influenced by the current density and mass-transfer coefficient. From a comparison of the results of the three electrodes it has been found that boron-doped diamond gives a faster oxidation rate and better current efficiency.     

Understanding aluminum behaviour in aqueous alkaline solution using coupled techniques: Part II: Acoustic emission study

This work focuses on the behaviour of pure aluminum in alkaline media, by coupling both acoustic emission (AE) and direct hydrogen voltammetry to electrochemistry. We notably monitored, recorded and analyzed the acoustic emission activity generated by the aluminum electrode as a function of its polarization during a linear sweep voltammetry (from anodic to cathodic potentials) on pure aluminum in 4 M aqueous potassium hydroxide solution. Such in situ coupling of electrochemistry and acoustic emission shows a perfect correlation between the two signals. After careful analysis of the AE signal using a statistical treatment, and based on five relevant AE parameters (rise time, duration, amplitude, absolute energy, maximum frequency), we could separate various groups of AE signals occurring at the aluminum electrode. We further linked them to the different (and possibly concomitant) electrochemical phenomena, which are taking place upon polarization of the aluminum electrode in strong alkaline medium.First, we confirmed that hydrogen evolution initiates for potentials positive to aluminum open circuit potential in 4 M potassium hydroxide solution; such small but non-negligible hydrogen production occurs in parallel to aluminum oxidation. Second, aluminum oxides are present only around the open circuit potential; whereas they are eroded for high aluminum oxidation potentials, they are flaked off at high hydrogen evolution potentials. Such latter process is probably accelerated by the hydrogen evolution-induced alkalization of the electrolyte. Third, two modes of hydrogen evolution are recorded: one on the oxide, the other one on bare aluminum, the latter being the most efficient. This strong hydrogen evolution at very low electrode potential probably assists the removal of the brittle residual oxide/passive film present on aluminum (which we denote as hydrogen-assisted aluminum exfoliation corrosion), therefore causing the rapid erosion of the aluminum electrode. As a result, aluminum is never in immunity conditions in strong alkaline medium.     

Cement composition and sulfate attack: Part I

Four cements were used to address the effect of tricalcium silicate content of cement on external sulfate attack in sodium sulfate solution. The selected cements had similar fineness and Bogue-calculated tricalcium aluminate content but variable tricalcium silicates. Durability was assessed using linear expansion and compressive strength. Phases associated with deterioration were examined using scanning electron microscopy and X-ray diffraction. Mineralogical phase content of the as-received cements was studied by X-ray diffraction using two methods: internal standard and Rietveld analysis.The results indicate that phase content of cements determined by X-ray mineralogical analysis correlates better with the mortar performance in sulfate environment than Bogue content. Additionally, it was found that in cements containing triclacium aluminate only in the cubic form, the observed deterioration is affected by tricalcium silicate content. Morphological similarities between hydration products of high tricalcium aluminate and high tricalcium silicate cements exposed to sodium sulfate environment were also observed.     

Experimental investigation and numerical modeling of carbonation process in reinforced concrete structures: Part II. Practical applications

The mathematical-numerical method developed by the authors to predict the corrosion initiation time of reinforced concrete structures due to carbonation process, recalled in Part I of this work, is here applied to some real cases. The final aim is to develop and test a practical method for determining the durability characteristics of existing buildings liable to carbonation, as well as estimating the corrosion initiation time of a building at the design stage. Two industrial sheds with different ages and located in different areas have been analyzed performing both experimental tests and numerical analyses. Finally, a case of carbonation-induced failure in a prestressed r.c. beam is presented.     

Water electrolysis under microgravity: Part 1. Experimental technique

Water electrolysis was conducted in both alkaline (25 wt.% KOH, 2 wt.% KOH) and acid (0.1N H₂SO₄) solutions for 8 s under microgravity environment realized in a drop shaft. The gas bubble formation of hydrogen and oxygen on platinum electrodes was observed by CCD camera. In alkaline solutions, a bubble froth layer grew on the electrode surface. Hydrogen bubble size was smaller than that of oxygen. The current density at constant potential decreased continually with time. In spite of the growth of a bubble froth layer on the electrode, the electrolysis never stopped, apparently because fresh electrolyte is supplied to the electrode surface by microconvection induced by the gas bubble evolution. In acid solution, hydrogen gas bubbles frequently coalesced on the cathode surface, yielding a larger average bubble than that of oxygen. The current density did not vary at constant potentials from -0.4 to −0.8 V versus reversible hydrogen electrode (RHE), because the effective electrode surface area was significantly reduced by the larger bubble size compared to alkaline electrolyte. The present experiments indicate that, especially in a microgravity environment, the bubble evolution behavior and the resultant current-potential curves are significantly influenced by the wettability of the electrode in contact with the electrolyte.     

Electrochemistry of active chromium: Part II. Three hydrogen evolution reactions on chromium in sulfuric acid

It was shown that chromium in deaerated sulfuric acid exhibits two stable corrosion potentials, depending whether the metal had previously been in contact with air or subjected to activation by cathodically evolving hydrogen. Electrochemical polarization measurements, as well as measurements of the actual metal dissolution rate at the corrosion potentials, anodic or cathodic polarization, using the analytical determination of Cr ions in the solution, weight-loss of metal, or volumes of hydrogen evolved, showed that hydrogen can evolve on chromium by three different reaction mechanisms. The first one is the electrochemical hydrogen evolution reaction from H⁺ ions at the bare chromium surface obtained by cathodic activation. This reaction and the active anodic dissolution of chromium determine one stable corrosion potential. The second reaction is the reaction of H⁺ ions on the oxidized chromium surface which, coupled with the anodic dissolution of passivated chromium determines the other stable corrosion potential. The third one is the “anomalous” or chemical reaction of chromium with water molecules and hydrogen ions whereby hydrogen is liberated. This is a potential independent reaction, occurring on the bare metal surface, and which is at pH <2 several times faster at the corrosion potential than the electrochemical hydrogen evolution reaction. The consequence is that the overall corrosion rate is several times faster than that determined by the usual electrochemical methods. The applicability of the different methods of measuring electrochemical corrosion rates and cathodic current efficiencies in chromium plating is discussed. Also, a possible role of the “anomalous” chromium dissolution in corrosion fatigue and stress corrosion cracking of stainless steels is considered.     

Experimental investigation and numerical modeling of carbonation process in reinforced concrete structures: Part I: Theoretical formulation

In this work, the mathematical-numerical model of carbonation process in reinforced concrete (RC) structures, which has been developed by the authors, is applied to different cases of study to take into account the probabilistic nature of durability assessment procedure even if within the framework of a rough and ready approach. In particular, the aim of this Part I of the work is to study how the variability of the parameters defining the differential equations in the model influence the assessment of the corrosion initiation time of RC structure. Comparison with experimental results and numerical simulations are undertaken in Part II of this work.     

Surface electrochemistry of UO2 in dilute alkaline hydrogen peroxide solutions: Part II. Effects of carbonate ions

The electrochemical reduction of hydrogen peroxide has been studied on uranium dioxide electrodes. The reduction kinetics are found to be influenced by dissolved carbonate/bicarbonate ions. The formation of hydrated U^VI species on the electrode surface is avoided in carbonate solutions, allowing H₂O₂ reduction to proceed at less cathodic potentials than in carbonate-free solutions. At more cathodic potentials, the adsorption of carbonate ions on the active reduction sites inhibits the H₂O₂ reduction reaction. Over a narrow potential region, the reduction of peroxide is catalyzed by coadsoption of H₂O₂ and HCO₃⁻/CO₃²⁻. The pH dependence of the H₂O₂ reduction reaction appears to be stronger in carbonate solutions than in solutions that do not contain carbonate. This can be attributed to the displacement of inhibiting CO₃²⁻/HCO₃⁻ adsorbed ions by OH⁻.     

Development of a galvanic sensor system for detecting the corrosion damage of the steel embedded in concrete structure: Part 2. Laboratory electrochemical testing of sensors in concrete

The correlation between sensor output and the corrosion rate of steel bar was confirmed in concrete environment. Open-circuit potential, linear polarization resistance (LPR) measurement and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion behavior of steel bar embedded in concrete. Also, galvanic current measurements of designed sensors were conducted to obtain the charge of sensor embedded in concrete.In this study, the results of corrosion behavior of reinforcing steel showed a consistence among the data obtained by open-circuit potential monitoring, LPR and EIS measurements. Steel/copper sensor showed a good correlation in concrete environment between sensor output and corrosion rate of steel bar. However, there was no relationship between steel/stainless steel sensor output and corrosion rate of steel bar due to the low galvanic current output. Through the relationship between the steel/copper sensor output and the corrosion rate of reinforcing steel, the real corrosion damage of the reinforcing steel can be detected. Consequently, this confirms that the galvanic sensor system is a good method for detection of corrosion in reinforced concrete.     

Investigation of zinc chromatation: Part II. Electrochemical impedance techniques

A mechanism to explain the formation of a chromate layer on zinc is proposed. It assumes that a ZnO inner film blocks the zinc surface on which the chromate layer grows. This layer has gel-like properties. The diffusion of the protons across the chromate layer and across the solution is supposed to be the kinetically limiting steps. This model was derived and experimentally tested in terms of impedance. The influences of the immersion time, mass transport, and pH of the chromatation solution were examined. A rather good agreement was found between the predictions of the model and the experimental results.