Impact of transient chemistry on the corrosion potential of a steam turbine disc steel

The adoption of two-shifting in coal-fired power generation (switching from on-load to off-load conditions on a daily basis and off-load for the weekend) results in regular cycling of the solution chemistry of the condensed steam on the turbine discs. A first stage investigation has been made of the effect of such chemistry cycling on the corrosion potential of the disc steel. The corrosion potential is typically about +0.05 V (SCE) in off-load chemistry (aerated pure water) and below −0.6 V (SCE) in on-load chemistry (deaerated solution containing chloride or chloride and sulphate anions). The critical observation was the sluggish response of the corrosion potential upon restoration of deaerated on-load conditions with the implication of a likely increase in pit and stress corrosion crack development.     

Modeling the environmental dependence of pit growth using neural network approaches

Corrosion pits have been shown to nucleate fatigue cracks, and this is a critical issue for aerospace aluminum alloys, which experience a variety of corrosive environments in service. Consequently, modeling pit growth as a function of environment is necessary. In this study, two orientations of AA7075-T651 blocks were boldly exposed in solutions of varying temperature, pH, and [Cl⁻] for three exposure times. Optical profilometry and Weibull functions were utilized to characterize pit depth and diameter distributions. Artificial neural networks were a powerful tool in effectively modeling maximum pit dimensions and Weibull parameters. In most environments, pit growth followed t^1/3 kinetics.     

Initiation and repassivation of pitting corrosion of carbon steel in carbonated concrete pore solution

The initiation, propagation, repassivation of metastable pits of Q345 carbon steel in Cl⁻ containing concrete pore solution were studied by electrochemical noise. The initiation rate of metastable pits increases exponentially up to a constant value with time. After stable pit occurs, the nucleation of metastable pits is mainly induced by the rust layer, and mainly takes place in the outskirt of the rust layer. Stable pits incline to expand horizontally to produce a shallow pit. In addition, high concentration of nitrite can inhibit the nucleation of metastable pits around the rust cover and accelerate the repassivation of stable pits.     

The effects of molybdate and dichromate anions on pit propagation of mild steel in bicarbonate solution containing Cl

The effects of molybdate and dichromate anions on pit propagation of mild steel in bicarbonate solution containing Cl⁻ were investigated by electrochemical measurements. MoO₄²⁻ ion suppressed both pit nucleation and propagation. Cr₂O₇²⁻ ion suppressed pit nucleation, but stimulated pit growth. The different effects of the two anions on pit propagation were explained by the opposite effects on pH value within pits. The pH value in molybdate-containing solution increased as a result of polymerization of MoO₄²⁻, while in dichromate-containing solution, pH value decreased due to hydrolysis of Fe³⁺ and Cr³⁺ which are the products of oxido-reducing reactions between Cr₂O₇²⁻ and Fe²⁺ ions.     

Localised dissolution of iron in buffered and non-buffered chloride containing solutions

Pitting corrosion of pure iron was studied by using conventional samples, and artificial pit electrodes. Experiments were conducted in solutions of 0.01, 0.1 and 1 mol dm⁻³ NaCl at pH values of 7, 10, 11 and 12; and in borate buffer solutions with the same chloride concentrations and pH 8.7 and 9.2. Four times higher concentration of borate salt was required to reach inhibiting capacity of the hydroxyl anions, as determined via pitting potentials. From measurements of solution resistance, the increase in local conductivity due to dissolved corrosion products exuded from the pit was calculated for each bulk solutions. For the artificial pit electrodes, contribution of the borate species to the internal pit solution conductivity in low chloride solution was associated with the difference between transition potential, E_T, values for buffered and non-buffered solutions, and this contribution was also used to explain the non-linear dependence of E_T on [Cl⁻]. Further analysis was conducted using the concept of the critical i.x parameter for stable pit propagation.     

A model to predict the evolution of pitting corrosion and the pit-to-crack transition incorporating statistically distributed input parameters

A model based on deterministic equations with statistically distributed input parameters has been developed for simulating the evolution of the pit depth distribution at different exposure times and the percentage of pits that transform to stress corrosion cracks. The model has been applied to the specific case of steam turbine disc steel exposed to a range of environments under applied stress. With preliminary fitting at one exposure time, the simulation not only reflects the trends in the experimental measurement but also the model, uniquely, reproduces the statistical variability or “noise” associated with the measurements.     

Electrochemical short crack effect in environmentally assisted cracking of a steam turbine blade steel

Measurement has been made of the corrosion fatigue short crack growth rate in a 12Cr steam turbine blade steel subjected to low frequency trapezoidal loading in aerated and deaerated 300 ppb¹ Cl⁻ and 300 ppb ${\text{SO}}_4^{2-}$, simulating early condensate chemistry. No difference in growth rate compared to that for long cracks was observed in deaerated solution but significantly enhanced growth rate was obtained in aerated solution for a short crack of length less than 250 μm. Complementary stress corrosion cracking tests were conducted but to ensure crack development at modest applied stresses the environment adopted was aerated 35 ppm Cl⁻, representing a severe system upset. In this case, the growth rate of the short crack was up to 20 times higher than that for a long crack (>6 mm), even though the crack length had reached 1.6 mm. An explanation for both sets of data based on the difference in potential drop between a short and long crack is expounded.     

Comparative evaluation of environment induced cracking of conventional and advanced steam turbine blade steels. Part 2: Corrosion fatigue

Corrosion fatigue crack propagation rates have been determined for two steam turbine blade steels, PH13-8, a candidate steel for advanced turbines, and FV566, typical of conventional turbine blades. The testing was undertaken in simulated condensate environment, 300 ppb Cl⁻ and 300 ppb , at 90 °C using trapezoidal loading with a rise time of 20 min to simulate two-shifting (switching on- and off-load on a daily basis). Aerated and deaerated conditions were tested, the former being more representative of the retained aeration in the chamber as the system comes on load. In aerated solution at ΔK = 20 MPa m^1/2 the cyclic crack growth rate for the PH13-8 steel was about a factor of two lower than that for the FV566 steel but the reverse was true for deaerated solution. In both cases, the difference in growth rates diminished with increasing ΔK. Although the cyclic crack growth rate is high the number of cycles per annum is small and the direct impact on overall life may be modest, but not insignificant. The observed cracking behaviour is best explained by a hydrogen assisted cracking mechanism.     

Pit growth behaviour of aluminium under galvanostatic control

The pit growth process on (1 0 0) aluminium under anodic pulse current in a mixed solution of 1 M HCl and 0.1 M H₂SO₄ at 30 °C has been evaluated using potential transient measurements and pit size distributions obtained by scanning electron microscopy. Sustained pit growth is observed for all pits during the initial anodic potential rise before reaching a steady-state etch potential, whereas a substantial fraction of the pits passivate at the steady-state etch potential. The pit growth rate during the initial potential rise is 3.4 μm s⁻¹, which is similar to that at the steady-state etch potential. The growth rates of active pits are potential-independent.     

Corrosion behaviour of nano structured sol-gel alumina coated 9Cr-1Mo ferritic steel in chloride bearing environments

A stable boehmite sol was synthesized using Al-isopropoxide as a precursor in an appropriate ratio with water. Afterwards, the 9Cr-1Mo steel specimens were coated with prepared boehmite sol by dip coating technique. AFM analysis of the coated specimens confirmed the presence of nano sized particles (8-12 nm) in the coating. Electrochemical measurements like potentiodynamic and potentiostatic polarisations, electrochemical impedance spectroscopy (EIS) in different concentrations of Cl⁻ ions indicated that the sol-gel alumina coating is able to make an appreciable improvement in the corrosion resistance of the base alloy. It was also observed that the sol-gel coatings can control the pitting attack up to a certain extent in 100 ppm Cl⁻ containing solution. However, the coatings become susceptible towards pitting attack in 200 ppm Cl⁻ bearing solution. The SEM micrographs of the corroded surfaces revealed the occurrence of severe pitting on the uncoated specimens in 100 ppm Cl⁻ solution and also on the coated specimen in 200 ppm Cl⁻ solution.     

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.     

The kinetics of pit growth on alloy 600 in chloride solutions at high temperatures

Alloy 600 tube specimens were subjected to corrosion in de-aerated 0.1 M NaCl solution at 100–250°C at applied potentials more positive than the respective pit nucleation potentials, and in de-aerated 200 ppm CuCl₂ solution at 150 and 280°C under open circuit conditions. In NaCl, the pits grew in depth proportionally to t^0.3, t^0.5 and t^0.7 (t = time) at 100, 150 and 250°C, respectively. In CuCl₂ at both 150 and 280°C, the pit deepening rate was proportional to t^0.4. In both the solutions studied, the density of pits observed on the surface of specimens after the same time of corrosion at 100°C was less than at higher temperatures, whereas the pit depth was greater at 100°C than at higher temperatures. The morphology of pits was temperature dependent. The corrosion products accumulated on pit bottoms were enriched in Cr, Ti and S, and impoverished in Fe and Ni.     

Novel images of the evolution of stress corrosion cracks from corrosion pits

SCC in turbine disc steels exposed to simulated steam-condensate tends to nucleate preferentially from corrosion pit precursors. The evolution of these cracks is not straightforward and not well understood. In this work, unique three-dimensional X-ray microtomographic images have confirmed that cracks develop predominantly at the shoulder of the pit, near the pit/surface interface, for specimens stressed to 50–90% σ_0.2. In support of this observation, FEA of model pits indicate that strain is a maximum on the pit wall just below the pit mouth. Implications of these observations for the pit-to-crack transition and predictive-modelling of crack nucleation and growth are discussed.     

Effects of solution pH and Cl on electrochemical behaviour of an Aermet100 ultra-high strength steel in acidic environments

In this work, the effects of solution pH and Cl⁻ on the electrochemical behaviour of an Aermet100 ultra-high strength steel in 0.5 M (Na₂SO₄ + H₂SO₄) solution were studied by polarization curve and electrochemical impedance spectroscopy (EIS) measurements, combined with scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) characterization. The results show that, when solution pH is below 4, the steel is in the active dissolution state, and corrosion current decreases with the increase of pH. There exists a critical pH value, above which the steel is passivated. Moreover, the oxides and hydroxides of Fe, Co, Ni and Cr are the primary components of the passive film. With addition of Cl⁻, pits are initiated on the steel electrode.     

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.     

Nano-pit corrosion of the tabs in aluminum electrolytic capacitor: Polarization characteristics of the tabs in ethyleneglycol-borate solution with chloride ions

To evaluate the corrosion behavior of the anode tab in aluminum electrolytic capacitor, we performed some electrochemical and morphology analysis using the polarization curves in conjunction with atomic force microscope (AFM), scanning electronic microscope (SEM) and optical microscope (OM). The results suggest that the current oscillation was found to be associated with nano-pit, which is defined as the rectangular pit (β) with a depth less than 55 nm and a width no more than 100 nm. Furthermore, elevation of Cl⁻ concentration widened the crevices caused by electrolytic tension, enlarged the nano-pit area, and accelerated the electrochemical reaction rate of the anode tab in ethyleneglycol-borate solution. These findings may have implications for the failure of aluminum electrolytic capacitor.     

Corrosion behaviour of aluminium in copper containing environment

Corrosion behaviour of pure aluminium galvanically connected to metallic copper or in the presence of Cu²⁺ ions was investigated by electrochemical measurements in Na₂SO₄ and Na₂SO₄ + NaCl test solutions. It has been found that in aerated Cl⁻ ion containing solutions pitting corrosion of aluminium emerged immediately, while in the absence of oxygen this process was less violent. Effect of passivating pre-treatment of aluminium surface on corrosion behaviour Cu-Al bimetallic system is also demonstrated.     

Acoustic emission during pitting corrosion of 304 stainless steel

Acoustic emission (AE) during pitting corrosion of 304 stainless steel (304 SS) in H₂SO₄ solutions with different pH values and Cl⁻ concentrations was studied. Two types of AE signals are detected in all solutions. Each type of signals is characterized by AE parameters (rise time, counts number, duration and amplitude) and waveform carefully. It is believed that the hydrogen bubbles evolution inside the pits is the AE source.     

Explanation of the effect of high chloride concentration on the critical pitting temperature of stainless steel

We correlate the effect of high chloride concentration on the critical pitting temperature (CPT) of type 316L stainless steel with its effect on the critical pit solution chemistry as determined by the artificial pit technique. It is shown that the change in CPT with bulk chloride concentration (0.5-9 mol kg⁻¹) can be correlated with a change in the ratio of C^∗/C_s, where C^∗ is the critical dissolved alloy cation concentration to sustain pitting, and C_s is the solubility of FeCl₂ at the pit surface. A complicating factor is that natural pits can only grow with C^∗ = C_s at the lower chloride concentrations, but can grow without the salt film at very high chloride concentrations; this transition is believed to occur close to 5 or 6 m bulk chloride concentration. The dependence of C_s on bulk chloride concentration is given a new interpretation based on a common-ion effect operating within an altered local chemistry with complexation.     

Environmental factors affecting the corrosion behavior of reinforcing steel. IV. Variation in the pitting corrosion current in relation to the concentration of the aggressive and the inhibitive anions

The pitting corrosion current of reinforcing steel is measured under natural corrosion conditions in Ca(OH)₂ solutions in presence of Cl⁻ as aggressive ions and as inhibiting anions. The corrosion current starts to flow after an induction period which depends on solution composition (concentration, pH and presence or absence of the aggressive and the inhibiting anions). The limiting corrosion currents increase with increasing the Cl⁻ ion concentration and decrease with increasing the pH and inhibiting ions concentration. The inhibition efficiency of the studied inhibiting ions increases in the following order: , and depends on the way by which the inhibitor is added to the solution. Injection of the inhibiting anions in solution causes repassivation of the pre-formed pits through competition with Cl⁻ ions for adsorption sites on metal oxide surface. The adsorbability constant and the free energy of repassivation of the inhibiting anions are calculated.