Conditions for the onset of current oscillations at the limiting current of the iron electrodissolution in sulfuric acid solutions

The experimental conditions and parameters that control the transition from a steady to an nonsteady limiting current and vice versa in the anodic Fe dissolution are studied in sulfuric acid solutions by using a downward-facing Fe electrode. Periodic and chaotic current oscillations are observed at the beginning of the limiting current region within a fixed potential region by decreasing the sulfuric acid concentration, by increasing the Fe-disk rotation rate and by increasing a series external resistance. It is found that current oscillations emerge when theIR drop exceeds a critical value (IR)_crit. The latter depends on the hydrodynamic conditions pertaining to the system. This is realized by the differences appeared in the value of (IR)_crit on using a stationary or a rotating Fe electrode. The effect of hydrodynamic conditions is shown by additional experimental results obtained by using an upward-facing Fe electrode, by increasing the density and viscosity of the solution on addition of glycerol, and by altering the solution properties near the Fe surface on addition of halide ions. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the authors in English.     

FTIR spectroscopic characterization of Nafion®–polyaniline composite films employed for the corrosion control of stainless steel

Nafion®–polyaniline (PAn) composite films deposited by a two-step process on a stainless steel (SS) substrate were characterized in this study using Fourier transform infrared (FTIR) spectroscopy under various conditions employed to evaluate their anticorrosion properties. The SS|Nafion® electrode was first prepared by placing a certain amount of Nafion® on the SS substrate, and then polymerization of aniline was carried out potentiodynamically on the SS|Nafion® electrode. The SS|Nafion®–PAn electrodes subjected to both potentiodynamic polarization and open-circuit conditions in sulfuric acid solutions without and with chlorides appeared to have distinct differences in their FTIR spectra. It is proposed that under the electrochemical conditions used in this study, the PAn is mostly formed inside the Nafion® membrane with a high proportion of oligomers influencing the ionic transport through the membrane. The inhibition of pitting corrosion arises primarily from the enhanced permselectivity of the composite film due to the Nafion® membrane that prevents chloride transport. An essential beneficial effect comes also from the PAn redox properties on the growth of the passive oxide film. Even under severe corrosion conditions, Nafion®–PAn films retain their redox activity and chemical stability, whereas the membrane crystallinity seems to be enhanced.

     

FTIR spectroscopic characterization of Nafion®–polyaniline composite films employed for the corrosion control of stainless steel

Nafion?–polyaniline (PAn) composite films deposited by a two-step process on a stainless steel (SS) substrate were characterized in this study using Fourier transform infrared (FTIR) spectroscopy under various conditions employed to evaluate their anticorrosion properties. The SS|Nafion? electrode was first prepared by placing a certain amount of Nafion? on the SS substrate, and then polymerization of aniline was carried out potentiodynamically on the SS|Nafion? electrode. The SS|Nafion?–PAn electrodes subjected to both potentiodynamic polarization and open-circuit conditions in sulfuric acid solutions without and with chlorides appeared to have distinct differences in their FTIR spectra. It is proposed that under the electrochemical conditions used in this study, the PAn is mostly formed inside the Nafion? membrane with a high proportion of oligomers influencing the ionic transport through the membrane. The inhibition of pitting corrosion arises primarily from the enhanced permselectivity of the composite film due to the Nafion? membrane that prevents chloride transport. An essential beneficial effect comes also from the PAn redox properties on the growth of the passive oxide film. Even under severe corrosion conditions, Nafion???/em>PAn films retain their redox activity and chemical stability, whereas the membrane crystallinity seems to be enhanced.     

The effect of ionic and electronic properties of titanium oxide on the electrochemical growth and redox behavior of polyaniline on titanium surfaces

Polyaniline (PANI) was electrodeposited directly from aniline (ANI)-containing sulfuric acid media on Ti|TiO₂ electrodes, which were prepared in ANI-free 0.5 M H₂SO₄ solution by applying suitable anodization conditions in order to control the donor density (N _D) in the oxide layer of a fixed thickness. By using the suggested procedure, reproducible conditions for the cyclic voltammetric growth of PANI on Ti can be achieved, and most importantly, the properties of Ti|TiO₂|PANI electrodes can be modulated to meet the requirements for specific applications. The polymerization rate and the deposited amount of PANI were found to depend strongly on the N _D estimated by Mott-Schottky analysis. The redox behavior of the resulted Ti|TiO₂|PANI electrodes indicated differences in acid solutions as compared with the corresponding behavior of other PANI-modified metal surfaces. Analysis of the anodic and cathodic electrochemical response of the prepared Ti|TiO₂|PANI electrodes discloses the significant role of ionic and electronic properties of the intervening oxide between the metal support and PANI.     

Dynamical response of the sinusoidally perturbed electrodissolution/passivation of iron in sulfuric acid solutions: Entrainment,spike generation,and quasiperiodicity

The iron/sulfuric acid (Fe/2 M H(2)SO(4)) system exhibits periodic current oscillations of relaxation type within the potential transition region formed between the active and passive states of the iron electrode when it is polarized in the 2 M sulfuric acid solution. In the present work the dynamical response of the Fe/2 M H(2)SO(4) electrochemical oscillator is investigated when the applied potential at the iron electrode is sinusoidally perturbed. The behavior of the periodically perturbed Fe/2 M H(2)SO(4) oscillator differs significantly from the response of other forced oscillators, as the potential amplitude E(p) and the frequency ratio omega(p)/omega(0) vary. The omega(p) and omega(0) are the angular frequencies of the perturbed applied potential and the unperturbed oscillator, respectively. A special feature of its response is the appearance of a number of spikes, generated within the passive section of a periodic oscillatory cycle for omega(p)/omega(0)<2.9, for periods of the autonomous oscillator T(0) greater, similar 3 s. The number of the generated spikes depends on the amplitude and frequency of the perturbed applied potential as well as on the period of the autonomous oscillator. Spikes are not generated for omega(p)/omega(0)=1 and the system is harmonically entrained by the forcing frequency. However, when the system is subharmonically entrained for omega(p)/omega(0) close to 2, spike generation does occur. By increasing the perturbation frequency for omega(p)/omega(0) greater, similar 2.9 and T(0) greater, similar 3 s, or by decreasing the autonomous period for T(0)<3 s and all the omega(p)/omega(0)<2.9 ratios, the spike generation pattern, is replaced by a quasiperiodic pattern. The dynamical response of the perturbed Fe/2 M H(2)SO(4) electrochemical oscillator is characterized by using time-delay reconstructions of the attractors, Poincare maps, and Fourier power spectra.     

Corrosion processes of iron in acidic solutions associated with potential oscillations induced by chlorates and perchlorates

Potential oscillations appear under current-controlled conditions of the chlorate- and perchlorate-perturbed electrochemical Fe|H₂SO₄ system. The potential oscillates between the active and passive states of Fe. It is shown that this oscillatory phenomenon is associated with localized corrosion of Fe due to the generation of chlorides via the reduction of chlorates and perchlorates by ferrous ions. Ferrous ions are generated either during the active dissolution of bare Fe (low-potential state) or during the passivation of Fe (high-potential state) due to a H⁺-catalyzed chemical dissolution of the oxide. Potential oscillations can be utilized to detect and characterize pitting corrosion of Fe in acidic solutions because, under current-controlled conditions, the halide-free Fe|H₂SO₄ system does not exhibit any kind of oscillatory phenomena. Characterization of pitting corrosion becomes possible through the analysis of galvanodynamic and galvanostatic curves obtained at various concentrations of chlorates and perchlorates. The variation of the anion concentration and applied current influence the onset and features of the potential oscillations.     

On the mechanism initiating bursting oscillatory patterns during the pitting corrosion of a passive rotating iron-disc electrode in halide-containing sulphuric acid solutions

Bursting current oscillations (trains of current spikes interrupted by a steady-state passive current) were found to occur during the iron anodic polarization in halide-containing sulphuric acid solutions. These oscillations occur at potentials located within a partially passive state of the iron. The partially passive state appears at potentials more positive than the unstable passive-active transition region of the current-potential curve of the Fe|2 M H₂SO₄ system for halide concentrations approximately ranged between 20 and 50 mM. The bursting oscillations appear after a certain induction period which ranged from minutes to several hours. Experiments were conducted in which an external resistance was connected in series between the ground and the working electrode for the Fe|2 M H₂SO₄ + 30 mM Br⁻ system. The results demonstrate that the appearance of oscillations is closely related to an IR-drop mechanism operating during the pitting corrosion of Fe induced by halides. When an appropriate value of the external resistance was imposed in the system the induction period was entirely eliminated. Bursting oscillations appear at once after setting the potential at the desired value. These results provide strong evidence that during the anodic electrodissolution of iron in halide-containing sulphuric acid solutions bursting current oscillations will be induced even though the electrode seems to be in the partially passive state. This is expected to occur after the passage of an induction period during which the system acquires a critical value of the ohmic potential drop. Received: 20 October 1997 / Accepted: 2 January 1998