Mechanism of anodic oxidation of molybdenum in nearly-neutral electrolytes studied by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy

Anodic oxidation of molybdenum in weakly acidic, nearly neutral and weakly alkaline electrolytes was studied by voltammetric and electrochemical impedance spectroscopic measurements in a wide potential and pH range. Current vs. potential curves were found to exhibit two pseudo-Tafel regions suggesting two parallel pathways of the dissolution process. Electrochemical impedance spectra indicated the presence of at least two reaction intermediates. X-ray photoelectron spectroscopic (XPS) results pointed to the formation of an oxide containing Mo(IV), Mo(V) and Mo(VI), the exact ratio between different valence states depending on potential and pH of the solution. A physico-chemical model of the processes is proposed and a set of kinetic equations for the steady-state current vs. potential curve and the impedance response are derived. The model is found to reproduce quantitatively the current vs. potential curves and impedance spectra at a range of potentials and pH and to agree qualitatively with the XPS results. Subject to further improvement, the model could serve as a starting point for the optimization of the electrochemical fabrication of functional molybdenum oxide coatings.     

Estimation of kinetic and transport parameters by quantitative evaluation of EIS and XPS data

The relatively large number of adjustable parameters often precludes the unambiguous interpretation of electrochemical impedance spectra in terms of a unique kinetic model. In the present paper, the possibilities offered by a combination between in situ electrochemical impedance spectroscopic data and ex situ surface analytical information to improve the credibility of the estimates of the kinetic and transport parameters are discussed. Two electrode systems in which passive oxide films are formed—stainless steel in simulated pressurised water reactor coolant and tungsten in sulphate-fluoride solutions—are used as representative examples to demonstrate the different approaches taken to analyse the experimental data in terms of the Mixed-Conduction Model. Ways to extract information on the rate-limiting steps of the process of passive film formation, growth and restructuring by quantitative comparison of the model equations to electrochemical impedance and X-ray photoelectron spectroscopic data are described and the significance of the obtained parameters for the kinetics of the overall process of metal and alloy dissolution in the passive state is discussed.     

X-ray absorption near edge structure and X-ray photoelectron spectroscopy studies of chloride in passive oxide films

X-ray absorption near edge structure (XANES), utilizing both electron yield and X-ray fluorescence detectors, and X-ray photoelectron spectroscopy (XPS) were used to follow chloride uptake by oxide-covered aluminum in 0.1 M NaCl solutions. The aluminum samples were polarized at selected potentials below (less positive than) the pitting potential. The electron yield XANES and XPS showed multiple peaks. The XPS chloride spectra showed two distinct sets of doublets. One doublet is related to chloride on the surface and the second is related to chloride incorporated in the oxide film. The XANES results also showed two peaks which are attributed to chloride on the surface and in the bulk of the oxide.     

An in situ electrochemical impedance spectroscopy/synchrotron radiation grazing incidence X-ray diffraction study of the influence of acetate on the carbon dioxide corrosion of mild steel

A combination of electrochemical impedance spectroscopy (EIS) and in situ synchrotron radiation grazing incidence X-ray diffraction (SR-GIXRD) has been used to study the influence of acetate on the carbon dioxide corrosion of mild steel. The SR-GIXRD data demonstrated that normal corrosion - in a carbon dioxide saturated brine - induced the formation of a thick corrosion scale of Fe₂(OH)₂CO₃ and Fe₂O₂CO₃, and this totally obscured the α-Fe diffraction peaks of the underlying steel substrate after 24 h. On the other hand, the carbon dioxide corrosion of mild steel in the presence of acetate also detected the Bragg diffraction peaks for Fe₂(OH)₂CO₃ and Fe₂O₂CO₃; however, the α-Fe diffraction peaks of the underlying steel substrate were not extinguished with time, and there was a reversal in the pattern of evolution of the intensities of the Fe₂(OH)₂CO₃ and Fe₂O₂CO₃ phases in acetate. Accordingly, the EIS data showed a poorly defined medium frequency time constant for the corroded steel specimen in brine spiked with acetate, and this medium frequency time constant was extinguished as a function of time. Alternatively, EIS of the corroded specimen also revealed a medium frequency time constant after 24 h. In addition, EIS complex-plane impedance plots showed that the corroded electrode had become passivated in an acetate-spiked brine, as evidenced by a three-fold enhancement in the charge transfer resistance at low frequency. These EIS/SR-GIXRD outcomes suggest that acetate affects the crystallization chemistry of the Fe₂(OH)₂CO₃/Fe₂O₂CO₃ corrosion scale, and this causes a mild passivation of the corroded steel surface.     

Electrochemically induced self-assembly of alkanethiolate adlayers on carbon steel in aqueous solutions

The electrochemical behavior of carbon steel was studied in near neutral buffered aqueous solutions saturated with mercaptoundecanoic acid (MUA) and dodecanethiol (DT) by using electrochemical techniques combined with X-ray photoelectron spectroscopy (XPS). MUA and DT adsorb on the Fe surface by cathodization in the potential range corresponding to the hydrogen evolution reaction by forming thiolate bonds. The presence of the adsorbate layer in contact with an extremely low amount of thiols in the neutral solutions hinders the hydrogen evolution reaction and prevents the formation of the iron oxides in a wide potential range.     

Chemical reactivity of thermo-hardenable steel weld joints investigated by electrochemical impedance spectroscopy

The chemical reactivity of oxide-free weld joints made of thermo-hardened carbon steel in different electrolytes was investigated by chronopotentiometry, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The objective was to identify the role of different electrolyte constituents on the electrochemical behaviour of the different materials constituting the weld joint, namely the weld material, the heat affected zone (HAZ) and the base carbon steel. Hardness measurements by Vickers and nano-indentation techniques indicated that the weld material is harder than the heat affected zone and the base carbon steel due to a Widmanstätten ferrite-type structure of the weld. Electrochemical measurements were performed on polished cross-sections on these weld joints in four electrolytes containing different additives. The weld joints are active in all tested electrolytes and the composition of the electrolytes dictates the dissolution even though the main chemical reactivity mechanism remains unaffected. A balanced presence of oxidative agent, inhibitor and HF in the electrolyte is necessary to obtain a homogeneous chemical attack on weld joint and Si-rich inclusion removal in weld material, while avoiding excessive attack roughening and/or pitting of the carbon steel.     

Passivity and pitting of carbon steel in chromate solutions

The passivity and pitting behavior of A516-70 carbon steel in chromate solutions were studied using electrochemical measurements. The anodic Tafel slopes in the active region show that carbon steel dissolution involves two mechanisms in this range: formation and further oxidation of a pre-passive film of Fe(OH)₂. The first current peak at −0.228 V (Ag | AgCl) in cyclic voltammograms is caused by the oxidation of the pre-passive film and the formation of a stable passive film of Cr³⁺+Fe³⁺. The second peak at 0.612 V is ascribed to the oxidation of Cr³⁺ in passive film to Cr⁶⁺. The charge-transfer step at the electrode/solution interface controls the film formation and dissolution; the role of diffusion is negligible. Chromate ions play a prominent role in the formation of passive film, but hardly affect the stability of the passive state. More chromate ions in solution enhance the dissolution of Cr³⁺ at the second peak potential. Upon addition of chloride ions metastable pits are initiated, as indicated by a typical current transient: a quick current rise followed by a slow recovery. A maximum exists in the potential dependence of the pit initiation rate. Metastable pit growth is controlled by the ohmic potential drop mainly across the cover over the pits. Increasing potential is beneficial to the repassivation of metastable pits, as indicated by the decreasing average repassivation time. A pit stabilization criterion, the ratio of peak pit current to pit radius, must exceed 6×10⁻² A cm⁻¹ during pit growth to avoid repassivation in the present system.     

Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy

Polyaniline (PANI) film electrodeposited in HCl medium using cyclic voltammetry (CV) with an upper potential limit of 0.90 V, exhibited an inductive behavior. PANI films deposited with different conditions were subjected to various applied potentials and the impedance characteristics were recorded through electrochemical impedance spectroscopy (EIS). The impedance results clearly reveal the existence of inductive behavior to PANI. Inductive behavior was observed for PANI films deposited with conditions which favor benzoquinone/hydroquinone (BQ/HQ) formation and further evidenced by X-ray photoelectron spectroscopy (XPS). A comparative analysis of the EIS and XPS results of PANI films prepared under similar conditions with the upper potential limits of 0.75 and 0.90 V, respectively, clearly documented that the presence of BQ/HQ, the degradation product of PANI, formed during the electrochemical polymerization at the upper potential limits causes inductive behavior to PANI.     

sp/sp characterization of carbon materials from first-principles calculations: X-ray photoelectron versus high energy electron energy-loss spectroscopy techniques

We have performed X-ray photoelectron spectroscopy (XPS) and high energy electron energy-loss spectroscopy (HEELS) calculations from first principles on a series of Monte Carlo generated amorphous carbon materials and have used a technique which separates the π* and σ* components of the energy-loss near-edge structure spectra of carbon materials on the basis of the ab initio electronic structure calculations of graphite to determine the sp³ fraction of the carbon systems. While the XPS technique is found to probe the local coordination geometry, the sp³ fractions resulting from the HEELS technique are found to be in very good agreement with those based on the π-orbital axis vector analysis which accounts for the effects of non-planarity in 3-coordinated systems.     

Oxide formation and conversion on carbon steel in mildly basic solutions

Surface oxide film growth and conversion processes on carbon steel were studied using a range of electrochemical techniques and ex situ surface analyses. The electrochemical study included (i) cyclic voltammetry as a function of various scan conditions and (ii) 7-day potentiostatic oxidation at a range of potentials while periodically performing Electrochemical Impedance Spectroscopy. Carbon steel surfaces at various stages of electrochemical oxidation were examined by SEM, Raman and X-ray photoelectron spectroscopy (XPS). These studies yield a consistent picture of film formation/conversion processes on carbon steel at pH 10.6, which is different to that reported for basic solutions (pH > 13). Oxide film formation/conversion mechanisms for three potential regions are proposed. In region I (≤−0.6 V vs SCE), the main oxide formed is Fe₃O₄ which grows via a solid-state process; in region II (−0.5 V ≤ E (vs SCE) ≤ −0.2 V), continuous growth of the Fe₃O₄ layer is accompanied by its anodic conversion to a more maghemite (γ-Fe₂O₃)-like phase near, or at, the oxide/solution interface by a similar solid-state mechanism to that described for region I; in region III (0.0 V < E (vs SCE) < 0.4 V), the anodic conversion of this Fe₃O₄/γ-Fe₂O₃ oxide to γ-FeOOH leads to a significant structural change, which can lead to film fracture and the introduction of enhanced transport pathways in the film.     

X-ray absorption near-edge structure and photoelectron spectroscopy of single-walled carbon nanotubes modified by a HBr solution

X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron spectroscopy (PES) have been used to investigate single-walled carbon nanotubes (SWNTs) modified by immersion in a HBr solution at room temperature. After treatment XANES spectra of SWNTs show a new pronounced feature, which has been assigned to new bonds between the sidewall of the SWNTs and Br atoms. This investigation demonstrates the unique capabilities of the XANES spectroscopy as a tool to achieve structural and bonding information of carbon nanotubes induced by chemical processes.     

Characterization by electrochemical impedance spectroscopy of magnetite nanoparticles supported on carbon paste electrode

Magnetite nanoparticles were supported on carbon paste electrode and characterized by low scan rate voltammetry and electrochemical impedance spectroscopy (EIS) to obtain mechanistic information related to its oxidation and reduction in acid media.The voltammograms showed only one reduction and one oxidation peak for the supported magnetite, which were attributed to formation of ferrous ion and ferric oxide, respectively. Both peaks are fairly wide, indicating complex mechanisms.Using EIS, a mechanism showing up to three time constants, capacitive all of them, was evidenced, both in anodic and cathodic domain. These were attributed to charge transfer at the highest frequencies, adsorption of generated species at intermediate frequencies, and proton adsorption at low frequencies. Discussion about the nature of the adsorbed species and the concerned mechanism for each domain is developed.     

Effects of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels in acidic chloride solutions

The role of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels was investigated in 0.5 M H₂SO₄, 3.5% NaCl and 0.5 M H₂SO₄ + 0.5 M NaCl solutions using potentiodynamic polarization, electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy techniques. The passive film stability was enhanced in 0.5 M H₂SO₄ and the pitting resistance was improved in 3.5% NaCl solution by more nitrogen addition. The influence of nitrogen extended the whole anodic polarization region in 0.5 M H₂SO₄ + 0.5 M NaCl solution, as demonstrated by the enhanced dissolution resistance, promoted adsorption and passivation process, improved film protection and pitting resistance with increasing nitrogen content. Possible mechanisms relating to the role of nitrogen in different potential regions were discussed.     

X-ray photoelectron spectroscopic studies of carbon fiber surfaces VIII—A comparison of type I and type II fibers and their interaction with thin resin films

Type I (high-modulus HM) and Type II (high-strength HT) carbon fibers electrochemically treated in a variety of electrolytes have been analyzed using X-ray photoelectron spectroscopy. A comparison of the differences in surface functionality and the possible interaction of treated fibers with epoxy resin is reported. The amount of carbon/oxygen functionality is greater for type II for the untreated and electrochemically treated fibers. Carboxylic/ester groups are produced at edge sites in the fiber surface whereas keto-enol groups are produced on the basal planes. Conclusive evidence for a chemical reaction between the fiber surface and 828-resin for fibers polarized in acidic electrolyte is given. It is not possible to conclude whether chemical bonding is responsible for the increased interlaminar shear strength of composites produced from treated fibers.     

Mechanistic study of the reduction of copper oxides in alkaline solutions by electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy was used to study the mechanism by which copper oxides are reduced in alkaline solutions. For the reductions of CuO and Cu₂O, a capacitive loop and also an inductive loop under certain conditions were observed in the complex plane. The electrochemical impedance for CuO reduction was not greatly dependent on the solution alkalinity and the kind of alkali hydroxide. However, the electrochemical impedance for Cu₂O reduction was considerably affected by the kind and concentration of alkali hydroxide. The diameter of the capacitive loop, i.e., the charge-transfer resistance (R_ct), was increased with increase in solution alkalinity. It should also be noted that R_ct was increased in the order of KOH < NaOH < LiOH. These dependences were consistent with the good separation between the reduction potentials of CuO and Cu₂O in chronopotentiometric and voltammetric measurements with strongly alkaline electrolytes containing Li⁺. The inductive loop observed for the Cu₂O reduction at higher concentrations of KOH (>6 M) and LiOH (>0.2 M) suggested the existence of an intermediate species (probably CuOH). The specific inhibitory effect of Li⁺ ions on the reduction of Cu₂O might be explained by a possible stabilization of CuOH by Li⁺ ions.     

Influence of temperature, chloride ions and chromium element on the electronic property of passive film formed on carbon steel in bicarbonate/carbonate buffer solution

The influences of temperature, chloride ions and chromium element on the electronic property of passive film formed on carbon steel in NaHCO₃/Na₂CO₃ buffer solution are investigated by capacitance measurement and electrochemical impedance spectroscopy (EIS). The results show that the passive film appears n-type semiconductive character; with increasing the solution temperature, the addition of chromium into carbon steel and increasing the concentration of chloride ions, the slopes of Mott–Schottky plots decrease, which indicates the increment of the defect density in the passive film. EIS results show that the transfer impedance R₁ and the diffusion impedance W decrease with increasing the solution temperature, with the addition of chromium into carbon steel and with increasing the chloride ions concentration. It can be concluded that the corrosion protection effect of passive film on the substrate decreases with increasing the solution temperature, adding chromium into carbon steel and increasing chloride ions concentration.     

Cyclability study of silicon–carbon composite anodes for lithium-ion batteries using electrochemical impedance spectroscopy

The effects of carbonization process and carbon nanofiber/nanotube additives on the cycling stability of silicon–carbon composite anodes were investigated by monitoring the impedance evolution during charge/discharge cycles with electrochemical impedance spectroscopy (EIS). Three types of Si–C anodes were investigated: the first type consisted of Si nanoparticles incorporated into a network of carbon nanofibers (CNFs) and multi-walled carbon nanotubes (MWNTs), with annealed polymer binder. The second type of Si–C anodes was prepared by further heat treatment of the first Si–C anodes to carbonize the polymer binder. The third Si–C anode was as same as the second one except no CNFs and MWNTs being added. Impedance analysis revealed that the carbonization process stabilized the Si–C anode structure and decreased the charge transfer resistance, thus improving the cycling stability. On the other hand, although the MWNTs/CNFs additives could enhance the electronic conductivity of the Si–C anodes, the induced inhomogeneous structure decreased the integrity of the electrode, resulting in a poor long term cycling stability.     

Review study of electrochemical impedance spectroscopy and equivalent electrical circuits of conducting polymers on carbon surfaces

Electrochemical impedance spectroscopy (EIS) is an experimental method for characterizing electrochemical systems. This method measures the impedance of the concerned electrochemical system over a range of frequencies, and therefore the frequency response of the system is determined, including the energy storage and dissipation properties. The aim of this article is to review articles focusing on electrochemical impedance spectroscopic studies and equivalent electrical circuits of conducting polymers, such as polypyrrole, polycarbazole, polyaniline, polythiophene and their derivatives, on carbon surfaces. First, the conducting polymers are introduced. Second, the electrochemical impedance spectroscopic method is explained. Third, the results of EIS applications using equivalent electrical circuits for conducting polymers taken from the literature are reviewed.     

Phase angle analysis for stress corrosion cracking of carbon steel in fuel-grade ethanol: Experiments and simulation

The stress corrosion cracking (SCC) of carbon steel in simulated fuel-grade ethanol (SFGE) was investigated using electrochemical impedance spectroscopy (EIS) and slow strain rate test (SSRT). Phase angle at low frequency range (<1 Hz) is sensitive to SCC process of carbon steel in SFGE. Phase angle decreases during an active crack growth. Frequency at maximum phase angle also increases towards an active cracking region at around 1 Hz. A transmission line model (TLM) is used to simulate the EIS response for SCC based on real geometrical parameters. By systematically changing the values of the circuit elements, the activities of the sample surface, crack tip and crack wall were studied in detail. By comparing the Bode plots from both experiment and simulation during SCC, a detailed mechanistic picture is derived to describe the behavior of the stress corrosion crack on carbon steel in the fuel-grade ethanolic environment.     

Study of the effect of magnesium concentration on the deposit of allotropic forms of calcium carbonate and related carbon steel interface behavior

Different allotropic forms of calcium carbonate scales were electrochemically deposited on a carbon steel surface in artificial underground Tunisian water at −0.95 V_SCE and various Mg²⁺ concentrations. Because of the importance of the diffusion process, the rotating disk electrode was used. The deposition kinetics were analyzed by chronoamperometry measurements and the calcareous layers were characterized by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The physical model proposed by Gabrielli was used to analyze the EIS measurements. Independent of the deposited allotropic form of calcium carbonate, the measurements showed that the oxygen reduction occurs in the pores formed between the CaCO₃ crystals and the metallic surface.