Determination of electrochemical parameters and corrosion rate for carbon steel in un-buffered sodium chloride solutions using a superposition model

Corrosion of carbon steel in un-buffered NaCl solutions was studied applying linear potential sweep technique to a rotating disk electrode. Current-potential curves were obtained from linear potential sweep at a rate of 1 mV s⁻¹ in solution with concentrations in the range 0.02-1 M NaCl and rotation rates in the range 170-370 rad s⁻¹, at 22 °C. Potential sweeps, which were conducted in the potential range −700 to −100 mV/SHE, were started from the cathodic limit in order to approach the measurement of corrosion under rust-free conditions. Polarization curves were analyzed with a superimposition model developed ad hoc and implemented in a computer program, which enabled determining the corrosion rate and kinetics parameters of the underlying anodic and cathodic sub-processes. The anodic sub-process, dissolution of iron, was well described in terms of a pure charge transfer controlled reaction, while the cathodic sub-process, oxygen reduction on iron, was well described in terms of mixed mass transfer and charge transfer control. Increase of electrode rotation rate increases the limiting current of oxygen reduction, which results in an enhanced corrosion rate of carbon steel. Increase of NaCl concentration has a dual effect: the limiting current of oxygen reduction decreases as a result of the influence of NaCl concentration on solution viscosity and the anodic dissolution of iron increases due to the influence of NaCl on pitting formation. However, this last mechanism predominates and a net increase in carbon steel corrosion rate is observed in this case.     

Corrosion of low carbon steel in atmospheric environments of different chloride content

This investigation aims to analyze the effect of Cl⁻ ion on the atmospheric corrosion rate of carbon steel. The metal samples were exposed to a marine atmospheric environment (95 and 375 m from the sea line) as well as an industrial atmospheric environment. The effects of Cl⁻ ions on the protective characteristics of the rust layers were assessed by IR spectroscopy, SEM-EDAX analyses, linear polarization resistance and electrochemical impedance spectroscopy (EIS). The results show that Cl⁻ ion influences the corrosion rate, as well as the morphology and composition of the rust layer.     

Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

Correlation between corrosion rate and AE signal in an acidic environment for mild steel

The AE method is an effective technique for inspecting corrosion damage of mild steel, such as tank bottom floors. However, the correlation between AE signals and corrosion behaviour for mild steel has not yet been fully clarified. In the present study, the authors considered that the corrosion regions of bottom floors become a strong acid environment by Cl⁻, as reported in a previous study. Thus, the polarization resistance for the test pieces of mild steel was measured with an AC impedance method under a strong acid environment. It was clear that the polarization resistance indicated the corrosion rate for a test piece of mild steel in the experiments. While measuring the AE signals, the corrosion rate was monitored with a test piece. As a result, the AE signal showed good correlation with the corrosion rates of the test pieces. The corrosion behaviour of the test pieces was then discussed with the corrosion potential measured during the experiments. Furthermore, the cathode current was changed to control the generated hydrogen gas volume. The volume of the hydrogen gas generated from the cathode reaction was correlated to the AE signals.     

Corrosion behaviour of low-carbon bainitic steel under a constant elastic load

The corrosion behaviour of low-carbon bainitic weathering steel in an environment containing chlorine ions (Cl⁻) was studied by applying different constant elastic loads. The results showed that the applied elastic load reduces the resistance of the rust layer to Cl⁻ diffusion because of the porous structure as well as the enhanced anion selectivity in the rust: this leads to more severe corrosion of the steel compared with load-free conditions. The corrosion rate increased with increasing loads. Corrosion enhancement can be attributed to mechanical-chemical interactions at the steel surface.     

Optimization of the pulsed current gas tungsten arc welding (PCGTAW) parameters for corrosion resistance of super duplex stainless steel (UNS S32760) welds using the Taguchi method

In the present work, a design of experiment (DOE) technique, the Taguchi method, has been used to optimize the pulsed current gas tungsten arc welding (PCGTAW) parameters for the corrosion resistance of super duplex stainless steel (UNS S32760) welds. A L₉ (3⁴) orthogonal array (OA) of Taguchi design which involves nine experiments for four parameters (pulse current, background current, % on time, pulse frequency) with three levels was used. Corrosion resistance in 3.5%NaCl solution was evaluated by anodic polarization tests at room temperature. Analysis of variance (ANOVA) is performed on the measured data and S/N (signal to noise) ratios. The higher the better response category was selected to obtain optimum conditions. The optimum conditions providing the highest pitting potential were estimated. The optimum conditions were found as the second level of pulse current (120 A), second level of background current (60 A), third level of % on time (80) and third level of pulse frequency (5 Hz). Under these conditions, pitting potential was predicted as 1.04 V_SCE that was very close to the observed value of 1.06 V_SCE. As a result of Taguchi analysis in this study, the pulse current was the most influencing parameter on the corrosion resistance and the background current had the next most significant effect. The percentage contributions of pulse current, background current, % on time, and pulse frequency to the corrosion resistance are 66.28%, 25.97%, 2.71% and 5.04%, respectively. Consequently, the Taguchi method was found to be promising technique to obtain the optimum conditions for such studies. Moreover, the experimental results obtained confirm the adequacy and effectiveness of this approach.     

Effects of strain on the corrosion behaviour of X80 steel

The effects of strain on the corrosion behaviour of X80 steel in 0.62 M NaCl aqueous solution were investigated in the present paper. An increase in strain causes the corrosion resistance of the specimen to present a down and up trend, with the lowest point at about 1.0 × 10⁻³. When the strain increases further, corrosion resistance decreases again until the strain reaches 5.5 × 10⁻³. After that, corrosion resistance improves with the increase in strain and tends to be relatively stable. The variation of corrosion resistance has much to do with the surface activity and behaviour of dislocation on the surface of the specimen.     

Degradation mechanism of galvanized steel in wet-dry cyclic environment containing chloride ions

The wet-dry cyclic test of a galvanized steel (GI) and pure zinc (ZN), which simulates marine atmospheric environment, has been conducted to clarify the degradation mechanism of galvanized steel. The samples were exposed to alternate conditions of 1 h-immersion in a 0.05 M NaCl solution and 7 h-drying at 25 °C and 60%RH, and the corrosion was monitored for 10 days (30 cycles) using a two-electrode type probe. Simultaneously, the corrosion potential was measured every three cycles only during the immersed conditions. The reciprocal of polarization resistance R_p⁻¹ was taken as an index of the corrosion rate. Several sample plates of GI and ZN were exposed, together with the monitoring probes. They were removed from the test chamber at the end of 1st, 3rd, 9th, 18th, and 30th cycles of exposure and were analyzed for the corrosion products with XRD and laser Raman spectroscopy. Further, their cross sections were analyzed with FESEM-EDS. The FESEM photographs and elemental analysis of cross sections confirmed that the R_p⁻¹ value commences to decrease when the corrosion front reaches Zn-Fe alloy layers (boundary layers of zinc coating and steel substrate) due to localized nature of attack. A schematic model of degradation mechanism and the role of galvanic protection have been discussed.     

Local additional potential model for effect of strain rate on SCC of pipeline steel in an acidic soil solution

Stress corrosion cracking (SCC) behavior of X70 pipeline steel in an acidic soil solution was investigated by slow strain rate test, surface characterization, potentiodynamic polarization curve measurement and electrochemical hydrogen permeation technique. A local additional potential model (LAPM) was developed to illustrate the critical role of strain rate in SCC of the steel. According to LAPM, both density and mobility of local active spots on the steel surface, i.e., dislocation emergence point, increase linearly with strain rate. Generation of such active spots introduces an additional negative potential locally, affecting the electrochemical reaction and, consequently, the susceptibility of the steel to SCC. It is found that a maximum of the SCC susceptibility occurs at strain rate of 10⁻⁶ s⁻¹, which is associated with an enhanced hydrogen evolution due to the local additional potential (LAP) effect. When strain rate is sufficiently high to exceed 10⁻⁶ s⁻¹, the mobility of the dislocation emergence points is so fast that the reactive species in solution cannot combine with them for cathodic reaction, resulting in a decrease of the SCC susceptibility. Similarly, a maximum of hydrogen permeation current observed at the strain rate of 10⁻⁶ s⁻¹ is also attributed to the effect of strain rate on the density and mobility of dislocations in the steel. Diffusion of hydrogen atoms in a strained steel is through both body diffusion and dislocation diffusion, with the latter enhanced by an increasing strain rate. When strain rate is so high that the dislocation mobility is sufficiently fast, hydrogen atoms become incapable of catching up with the dislocations. As a result, the hydrogen diffusion is dominated by the body diffusion mode.     

Quantitative evaluation of general corrosion of Type 304 stainless steel in subcritical and supercritical aqueous solutions via electrochemical noise analysis

Electrochemical noise (EN) sensors have been developed to measure the corrosion rate of Type 304 stainless steel (SS) in subcritical and supercritical environments. The EN sensors were tested in flowing aqueous solutions containing NaCl and HCl at temperatures from 150°C to 390°C, a pressure of 25 MPa, and flow rates from 0.375 to 1.00 ml/min. The potential and coupling current noise were recorded simultaneously and the noise resistance (R_n) was calculated from the standard deviations in the potential and current records. We found that the inverse noise resistance correlated very well with the corrosion rate evaluated from separate mass loss experiments, and that both the inverse noise resistance and the average corrosion rate were functions of temperature and flow rate. In the temperature range from 200°C to 390°C, the corrosion rate was found to be proportional to the inverse noise resistance and hence the Stern-Geary relationship can be used to evaluate the corrosion rate. However, at 150°C, the relation between inverse noise resistance and corrosion rate significantly deviated from the Stern-Geary relationship. It was found that the deviation was related to the low corrosion rate of Type 304 SS and 150°C.     

Corrosion and Prevention '95

The corrosion behaviour of duplex stainless steel 2101 exposed to 0.1?wt-%NaOH, 5.0?wt-%H₂SO₄ and 6.0?wt-%FeCl₃ solutions was investigated with an electrochemical noise technique. The time records revealed salient features of the steel in the three solutions, and the corresponding corrosion morphologies were shown. The slopes of the power spectral density plots of current and potential noises were associated with the nature of corrosion attack. The corrosion rates in the three media were reflected by the noise resistance, presenting good correlation with the results from linear polarisation and electrochemical impedance spectroscopy.     

The effects of pharmaceutically active compound doxycycline on the corrosion of mild steel in hydrochloric acid solution

Corrosion inhibition of mild steel in hydrochloric acid solution by doxycycline has been studied by weight loss measurements, polarization resistance, Tafel polarization and electrochemical impedance spectroscopy. The inhibitor showed more than 95% inhibition efficiency at optimum concentration 9.02 × 10⁻⁴ M. Potentiodynamic polarization suggests that it is a mixed type of inhibitor. Electrochemical impedance spectroscopy was used to investigate the mechanism of corrosion inhibition. Thermodynamic parameters were calculated to investigate mechanism of inhibition. The compound follows Langmuir adsorption isotherm. AFM studies of mild steel surface with and without inhibitor were performed and calculated roughness also supported the inhibition data.     

Effect of heat treatment on H2S corrosion of a micro-alloyed C–Mn steel

The H₂S corrosion resistance of a C–Mn pipeline steel with three different microstructures has been evaluated using electrochemical techniques with a 3% wt. NaCl solution at 50 °C. Microstructures included martensite, ferrite, and ferrite + bainite. Electrochemical techniques included potenthiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and electrochemical noise (EN) measurements. Most of the tests lasted 24 h. All techniques showed that the highest corrosion rate corresponded to the steel with a martensitic microstructure; up to one order of magnitude higher than the corrosion rate for steels with a ferritic + bainitiic microstructure, whereas the steel with the ferritic microstructure showed the lowest corrosion rate. EIS tests showed that the corrosion process was under charge transfer control, whereas EN results indicated that the three steels exhibited a clear tendency towards a localized type of corrosion. However, for longer immersion times, the steel with a martensitic microstructure tended to exhibit a mixture of uniform and localized attack. Results were discussed in terms of grain size, grain boundary energy, amount and distribution of particles found in each steel.     

The initial stage of pitting corrosion on coated steels investigated by photon rupture in chloride containing solutions

A photon rupture method, film removal by a focused pulse of pulsed Nd-YAG laser beam irradiation, has been developed to enable oxide film stripping at extremely high rates without contamination from the film removal tools. In the present study, Zn-55mass%Al alloy and Al-9mass%Si alloy-coated steel specimens covered with protective nitrocellulose film were irradiated with a focused pulse of a pulsed Nd-YAG laser beam at a constant potential in 0.5 kmol m⁻³ H₃BO₃-0.05 kmol m⁻³ Na₂B₄O₇ (pH = 7.4) with 0.01 kmol m⁻³ of chloride ions to investigate the initial stage of localized corrosion. At low potentials, oxide films on both coated alloys were reformed after the nitrocellulose films were removed by this method. The oxide film formation kinetics follows an inverse logarithmic law, in agreement with Cabrera-Mott theory. However, at high potentials, localized corrosion producing corrosion products occurs at the area where nitrocellulose film was removed. Nevertheless, when the applied potential is less noble, the dissolution current of the Zn-55mass%Al-coated steel samples is higher than that of Al-9mass%Si-coated samples.     

Corrosion behavior of titanium-clad carbon steel in weakly alkaline solutions

The electrochemical polarization curves and corrosion potentials during long-term immersion of Ti, carbon steel, carbon steel tightened-Ti and Ti-clad carbon steel specimens were investigated in bentonite-contacting solution (mixture of sodium sulfate and sodium carbonate solutions), sodium sulfate solution and borate solution adjusted to pH=9.0-9.84. Ti and carbon steel were passivated during immersion in borate solution, while carbon steel was corroded in the solutions containing SO₄²⁻ ions. The immersion potentials of Ti-clad steel and steel-tightened Ti specimens were controlled by the corrosion potential of carbon steel (about 0 V vs. RHE at 298 K). The Ti side of the clad specimen was, therefore, polarized cathodically at this immersion potential, and this caused hydration of and/or hydrogen penetration into the oxide film, resulting in degradation of its barrier property. Furthermore, the cathodic current on the Ti side was partially coupled with the anodic current in the corrosion reaction on the carbon steel side, resulting in acceleration of the overall corrosion rate.     

Corrosion inhibition of carbon steel in tetra-n-butylammonium bromide aqueous solution by benzotriazole and Na3PO4

The corrosion inhibition behavior of benzotriazole, Na₃PO₄ and their mixture on carbon steel in 20 wt.% (0.628 mol l⁻¹) tetra-n-butylammonium bromide aerated aqueous solution was investigated by weight-loss test, potentiodynamic polarization measurement, electrochemical impedance spectroscopy and scanning electron microscope/energy dispersive X-ray techniques. The inhibition action of BTA or SP or inhibitors mixture on the corrosion of carbon steel is mainly due to the inhibition of anodic process of corrosion. The results revealed that inhibitors mixtures have shown synergistic effects at lower concentration of inhibitors. At 2 g l⁻¹ BTA and 2 g l⁻¹ SP showed optimum enhanced inhibition compared with their individual effects.     

Effect of calcium ions on pitting corrosion and inhibition performance in CO2 corrosion of N80 steel

The electrochemical impedance spectroscopy (EIS) and polarization resistance technique were used to investigate the susceptibility of N80 steel to pitting corrosion under stagnant condition and the corrosion behavior under flowing condition with/without precorrosion in 3% NaCl solution, in 3% NaCl + 1.5% CaCl₂ solution and in 4.6% NaCl solution (equivalent Cl⁻ concentration to 3% NaCl + 1.5% CaCl₂ solution) saturated by CO₂ at 57 °C. The results showed that under stagnant condition the initiation period of pitting corrosion decreased with increasing Cl⁻ concentration, but at the same Cl⁻ concentration, Ca²⁺ could prolong the initiation period. Under flowing condition the corrosion rate without stagnant precorrosion was bigger than that with precorrosion, and the corrosion rate with precorrosion in 3% NaCl solution was bigger than that in 3% NaCl + 1.5% CaCl₂ solution. Inhibition of quaternary alkynoxymethyl amine (IMC-80-Q) under stagnant condition showed that the optimum inhibitor concentration significantly increased with the increase of Cl⁻ concentration from 3% NaCl solution to 4.6% NaCl solution, and for the solutions with the same Cl⁻ concentration, adding Ca²⁺ did not change the optimum inhibitor concentration.     

Effects of temperature and aggressive anions on corrosion of carbon steel in potable water

Experiments on the corrosion of carbon steel in three kinds of artificial potable waters containing different concentrations of aggressive anions, Cl⁻ and , open to air in the temperature range from 5 to 60 °C were conducted using weight loss and electrochemical methods. The corrosion rate increased in proportion to the concentration of aggressive anions and with increasing temperature. At lower concentrations of aggressive anions and temperatures, the corrosion rate was lower and the corrosion potential was higher, at intermediate concentrations and temperatures, the corrosion rate increased logarithmically with decreasing potential, and at higher concentrations and temperatures, the corrosion rate was higher and the potential was lower. The corrosion behavior in potable water can be determined by the balance between inhibitive action of oxygen (passive film formation) and aggressive action of Cl⁻ and ions.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Environmental factors affecting the corrosion behavior of reinforcing steel III. Measurement of pitting corrosion currents of steel in Ca(OH)2 solutions under natural corrosion conditions

Using a simple electrolytic cell, the pitting corrosion current of reinforcing steel is measured in Ca(OH)₂ solutions in presence of chloride and sulfate as aggressive ions. Pitting corrosion current starts to flow after an induction period which depends on the concentration of both the aggressive and the passivating anions. The pitting corrosion current densities reach steady-state values which depend also on the type and concentration of the corrosive and passivating anions. The corrosive action of the aggressive species decreased in the order: SO₄²⁻ > Cl⁻. Corrosion of the steel is found to be governed by a single electron transfer reaction. Raising the temperature decreases the induction period associated with pit initiation and increases the corrosion current associated with pit propagation. From Arrhenius plots, the activation energies for both pit initiation and pit propagation in presence of chloride and sulfate ions are calculated.