Direct electrosynthesis of polyaniline–montmorrilonite nanocomposite coatings on aluminum alloy 3004 and their corrosion protection performance

Homogeneous and adherent polyaniline–montmorrilonite (MMT) nanocomposite coatings were electrosynthesized on aluminum (Al) alloy 3004 (AA 3004) by using the galvanostatic polarization method. The synthesized coatings were characterized by UV–Vis absorption spectrometry, Fourier transform infrared spectroscopy, X-ray diffraction patterns and scanning electron microscopy. The corrosion protection effect of the coatings was demonstrated by performing a series of electrochemical experiments of potentiodynamic and impedance measurements on Al in 3.5 wt% aqueous NaCl electrolytes. The corrosion current (i_corr) values decreased from 6.55 μA cm⁻² for uncoated Al to 0.102 μA cm⁻² for nanocomposite-coated Al under optimal conditions.     

Miniaturisierte elektrochemische Sensoren zur in-situ-Untersuchung der Spaltkorrosion in Modellsystemen

In-situ-investigation of crevice corrosion in model systems using miniaturized electrochemical sensors Measuring characteristics of miniaturized sensors for the determination of the parameters pH value, oxygen content, concentration of chloride ions and redox potential was tested and optimized with regard to the application in model crevices. The sensors were used for examinations of crevice corrosion in 0.1 molar and 1 molar solution of NaCl at the following alloys: X 20 Cr 13, X 2 CrNi 18 10, X 2 CrNiMoN 17 13 5, X 2 CrNiMoN 17 13 5*, X 2 CrNiMo CuN 20 25 6. Corrosion characteristic of the alloys and the change of crevice electrolyte without external polarization and with galvanostatic polarization (i = 10 μA/cm², i = 200 μA/cm²) were tested and discussed by the hand of the model concepts from Oldfield and Sutton [1]. In experiments with galvanostatic polarization the steels with increasing content of chromium or molybdenum showed a growing stability against crevice corrosion. The results showed that simultaneous measurements of the above mentioned chemical parameters of crevice electrolyte in connection with the corrosion potential can supply additional information about causes and mechanism of crevice corrosion.     

Analysis of the galvanostatic polarization method for determining reliable pitting potentials on stainless steels in crevice-free conditions

In this paper the potential of the galvanostatic polarization technique as accelerated method for determining the characteristic pit potentials on stainless steels in crevice-free conditions is examined. Measurement of the potential change as a function of time shows a maximum that agrees with the nucleation pit potential. Thereafter, a stationary potential is reached corresponding to the protection potential against pit. Possible limitations of this kind of measurements have been remedied by refinements in the test procedure and conditions. The state of the surface oxide film and the applied anodic current are two basic parameters that must be well defined because they govern the pitting susceptibility. It has been found that with applied anodic currents in the range 40–200 μA/cm² and with prior electrode exposures to solution between 30 and 60 min it is possible to obtain results in excellent agreement with the conventional potentiodynamic tests with the advantage of smaller data scattering and absence of crevice at electrode/holder interfaces. These effects are the result of the rapid pitting stimulated in the galvanostatic method. This implies a short duration of the experiment thus also favouring the elimination of the time-dependent crevice, which notoriously contributes to the poor reproducibility of pit potentiodynamic potentials. A detailed series of experiments have been conducted on several stainless steels and in different test conditions to validate the accuracy of the galvanostatic polarization method.     

An innovative specimen configuration for the study of Mg corrosion

Based on an analysis of galvanic corrosion research, the research reported herein was formulated to examine the measurement of polarisation curves for Mg to develop a methodology whereby reliable polarisation curves can be measured for Mg. Cathodic polarisation curves were measured for high purity Mg in 3.5% NaCl saturated with Mg(OH)₂ using three specimen types: (i) mounted specimens, (ii) specimens hung by fishing line and (iii) plug-in specimens. Cathodic polarisation curves were evaluated to yield the corrosion current density i_corr and the corresponding corrosion rate P_i, which was compared with the corrosion rate evaluated from hydrogen evolution measurements, P_H, and the corrosion rate evaluated by weight loss measurements, P_W. Mounted specimens produced values of corrosion rate, P_i, three times larger than values of corrosion rate, P_i, for plug-in specimens, attributed to crevice corrosion in the mounted specimens. Crevice corrosion in Mg is totally unexpected from prior research. The plug-in specimen configuration was designed to have no crevice and to allow simultaneous measurement of P_H and P_i; P_i was consistently less than P_H and indicated an apparent valence for Mg of 1.45 in support of the Mg corrosion mechanism involving the uni-positive Mg⁺ ion. The plug-in specimen has advantages for the study of Mg corrosion.     

Carbon steel corrosion under anaerobic–aerobic cycling conditions in near-neutral pH saline solutions – Part 1: Long term corrosion behaviour

A corrosion mechanism has been developed to describe tubercle formation along pipeline steels during successive anaerobic–aerobic cycles. Small concentrations of O₂ under nominally anaerobic conditions can lead to the separation of anodes and cathodes. Under subsequent aerobic conditions localized corrosion is then promoted by O₂ reduction on the general magnetite-covered surface. Subsequently, the conversion of magnetite to maghemite passivates the general surface, and focuses corrosion within one major tubercle-covered pit. On switching from aerobic to anaerobic conditions, corrosion is temporarily supported by the galvanic coupling of lepidocrocite (γ-FeOOH) reduction (to γ-Fe-OH·OH) to steel dissolution primarily within the tubercle-covered pit.     

Modeling pipeline crevice corrosion under a disbonded coating with or without cathodic protection under transient and steady state conditions

Underground steel pipelines are protected by coatings and cathodic protection (CP). The pipeline corrosion occurs when the coating is disbonded away from a defect or holiday to form a crevice and the corrosion rate varies temporally and spatially in the crevice. In the presence of dissolved oxygen (O₂) in soil ground water, a differential O₂ concentration cell may develop in the crevice because O₂ diffuses more readily into the crevice through the holiday than through the disbonded coating. CP can decrease or eliminate the O₂ concentration cell depending on the potential applied at the holiday. Since the coatings are usually non-conductive, CP is unable to protect the steel surface deep inside the crevice. The transport of dissolved O₂, and that of dissolved carbon dioxide (CO₂) if present, into the crevice through holiday can be key to determining the crevice corrosion rate. In this work, the transient and steady state behavior of the corrosion process is investigated. The effect of the cathodic portion of iron vs. ferrous ion redox reaction on the crevice corrosion rate, which is often neglected traditionally, is further studied. At steady state, the effect of dissolved O₂ on the crevice corrosion rate and the added effect of dissolved CO₂ are mathematically modeled.     

A newly synthesized glycine derivative to control uniform and pitting corrosion processes of Al induced by SCN anions - Chemical, electrochemical and morphological studies

A newly synthesized glycine derivative (termed GlyD), 2-(4-(dimethylamino)benzylamino)acetic acid hydrochloride, was used to inhibit uniform and pitting corrosion processes of Al in 0.50 M KSCN solutions (pH 6.8) at 25 °C. For uniform corrosion inhibition study, Tafel extrapolation, linear polarization resistance and impedance methods were used, complemented with SEM examinations. An independent method of chemical analysis, namely ICP-AES (inductively coupled plasma atomic emission spectrometry) was also used to test validity of corrosion rate measured by Tafel extrapolation method. GlyD inhibited uniform corrosion, even at low concentrations, reaching a value of inhibition efficiency up to 97% at a concentration of 5 × 10⁻³ M. Results obtained from the different corrosion evaluation techniques were in good agreement. This new synthesized glycine derivative was also used to control pit nucleation and growth on the pitted Al surface based on cyclic polarization, potentiostatic and galvanostatic measurements. The pitting potential (E_pit) and the repassivation potential (E_rp) increased by the addition of GlyD. Thus GlyD suppressed pit nucleation and propagation. Nucleation of pit was found to take place after an incubation time (t_i). The rate of pit nucleation and growth decreased with increase in inhibitor concentration. Morphology of pitting was also studied as a function of the applied anodic potential and solution temperature. Cross-sectional view of pitted surface revealed the formation of large distorted hemispherical and narrow deep pits. GlyD was much better than Gly in controlling uniform and pitting corrosion processes of Al in these solutions.     

Effect of Fe-Zn alloy layer on the corrosion resistance of galvanized steel in chloride containing environments

In this study, the effect of Fe-Zn alloy layer that is formed during galvanizing process on the corrosion behavior of galvanized steel has been investigated. The galvanostatic dissolution of galvanized steel was carried out in 0.5 M NaCl solution to obtain the Fe-Zn alloy layer on the base steel. The alloy layer was characterized to be composed of FeZn₁₃, FeZn₇ and Fe₃Zn₁₀ intermetallic phases, which constitute the zeta, delta1 and gamma layers of galvanized steel, respectively. It was observed that the alloy layer has similar cathodic polarization behavior but different anodic polarization behavior compared to galvanized steel. The anodic current plateau of alloy layer was up to 100 times lower than that of galvanized coating. Corrosion test performed in wet-dry cyclic condition has shown that the alloy layer has lower corrosion rate as compared to galvanized steel. From the results of corrosion test of alloy layer and base steel, it was concluded that Zn²⁺ has positive effect on the protectiveness of the zinc corrosion products. The measurement of surface potential over the alloy/steel galvanic couple has confirmed the galvanic ability of alloy layer to protect both the alloy layer itself and the base iron during initial stage of atmospheric corrosion.     

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.     

Polypyrrole coatings as a treatment for zinc-coated steel surfaces against corrosion

A single-step electropolymerization of pyrrole on zinc-coated steel electrodes in aqueous medium was investigated under several techniques (potentiodynamic, galvanostatic and potentiostatic modes) by using carboxylate salts, such as the citrate, the succinate, the oxalate, the malate and the tartrate. Adherent and homogeneous PPy coatings were obtained only with tartrate counter-ions.The corrosion behaviour of zinc-coated steel electrodes electrochemical modified by PPy films were estimated by open circuit potential and DC polarization in NaCl, HCl and H₂SO₄ aggressive solutions. The obtained results show that the PPy coatings increase the corrosion potential and reduce the corrosion current. The salt spray test results show that the PPy coating prepared under ultrasonic waves is more resistant than those obtained in normal conditions.     

Electrochemical aspects of exfoliation corrosion of aluminium alloys: The effects of heat treatment

Electrochemical approaches are used to investigate the exfoliation corrosion (EFC) of a 7XXX series aluminium alloy that has undergone different tempering treatments. EFC was produced under an artificial crevice at open circuit potential in neutral chloride solutions, and is found to be associated to current and potential transients. EFC was also produced under galvanostatic control conditions. Observations made through Scanning Electron Microscopy (SEM) suggest that these transients result from the progression of inter-granular cracks. Last, over-ageing heat treatments that are known to decrease both metal hardness and EFC sensitivity were found to decrease the number of transients.     

Application of the multichannel electrode method to monitoring of corrosion of steel in an artificial crevice

Crevice corrosion of iron was evaluated using the multichannel electrode method in which 10 individual working electrodes (WEs) of pure iron were embedded in resin, placed in an artificial crevice in the range from 0.5 mm to 2.0 mm, and immersed in 0.51 mol dm⁻³ NaCl solution. The WEs were connected to an electronic circuit which allowed galvanic coupling between them and measurement of their individual coupling current or open circuit potential. Time-transient of the spatial distribution of coupling current and open circuit potential showed sequential transition of the coupling current on WEs at the middle position of the crevice from cathode to anode. The WE near the opening of the crevice initially showed a large anodic current, then a decreasing the anodic current corresponding to the current transition of other WEs, and finally a large cathodic current coupled with the other anodic WEs in the crevice. The transition of coupling current was explained by the change in pH and concentration of dissolved oxygen in the crevice. Thickness of the gap of the artificial crevice affected the transition behavior of coupling current distribution. For example, slower current transition with smaller coupling current was found in the case of a narrower gap. Such properties were related to the introduction and consumption of dissolved oxygen in the crevice solution and the circulation of gap solution from/to the outside of the crevice.     

Influence of the microstructure and laser shock processing (LSP) on the corrosion behaviour of the AA2050-T8 aluminium alloy

The corrosion behaviour of AA2050-T8 was studied after polishing and after laser shock processing (LSP) treatment using the electrochemical microcell technique and the SVET. After polishing, pitting at constituent particles and intergranular corrosion were observed. By contrast, no intergranular corrosion developed after LSP. Microcell measurements revealed that LSP increases the pitting potential. SVET measurements revealed that local anodic currents are systematically lower on LSP-treated surfaces than on polished ones. The current density on the LSP-treated surface remains constant around 50 μA cm⁻² up to 123 min after immersion, while on the polished surface it reaches 200 μA cm⁻².     

Crevice corrosion of Q235 carbon steels in a solution of NaHCO3 and NaCl

The crevice corrosion of Q235 carbon steels in a solution of NaHCO₃ and NaCl was investigated mainly by electrochemical noise. Three stages of crevice corrosion were found and include an induction stage, a transformation stage and a stable development stage. Principal component analysis and hierarchical agglomerative cluster analysis were used to identify the crevice corrosion stages. The electrode area ratio of the outer to the inner part of the crevice (r) significantly influenced the occurrence and development of crevice corrosion. The induction stage time increased as r increased.     

Initiation and repassivation of crevice corrosion of type 444 stainless steel in chloride solution

Effects of chloride ion concentrations, solution temperature, and crevice-forming materials on the crevice corrosion of type 444 stainless steel were investigated using a potentiostatic method. Critical crevice potential (E_crev) and repassivation potential (E_r) of the creviced alloy decreased with an increase in chloride concentration [Cl⁻], satisfying the logarithmic relationship between E and [Cl⁻]. In addition, E_crev and E_r of the alloy with silicone crevice former were measured to be higher than those of the alloy with an EPDM (Ethylene Propylene Diene Monomer) crevice former, suggesting that silicone was more effective in preventing water from penetrating crevices between a stainless steel sheet and the crevice former. In electrochemical current transient measurements with an applied potential, the intensity of current transients corresponding to the initiation of metastable pits increased abruptly near the E_r of the alloy, indicating that the stability of crevice corrosion is associated with the initiation of metastable pits.     

Influence of the applied stress rate on the stress corrosion cracking of 4340 and 3.5NiCrMoV steels under conditions of cathodic hydrogen charging

Stress corrosion cracking (SCC) of as-quenched 4340 and 3.5NiCrMoV steels was studied under hydrogen charging conditions, with a cathodic current applied to the gauge length of specimens subjected to Linearly Increasing Stress Test (LIST) in 0.5 M H₂SO₄ solution containing 2 g/l arsenic trioxide (As₂O₃) at 30 °C. Applied stress rates were varied from 20.8 to 6 × 10⁻⁴ MPa s⁻¹. Both the fracture and threshold stress decreased with decreasing applied stress rate and were substantially lower than corresponding values measured in distilled water at 30 °C at the open circuit potential. The threshold stress values correspond to 0.03–0.08 σ_y for 4340 and 0.03–0.2 σ_y for the 3.5NiCrMoV steel. SCC velocities, at the same applied stress rate, were an order of magnitude greater than those in distilled water. However, the plots of the crack velocity versus applied stress rate had similar slopes, suggesting the same rate-limiting step. The fracture surface morphology was mostly intergranular, with quasi-cleavage features.     

Electrochemical behaviour of Ti–6Al–4V alloy and Ti in azide and halide solutions

Electrochemical techniques including open circuit potential measurement, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion and passivation behaviour of Ti–6Al–4V alloy in sodium azide (NaN₃) solutions compared to the behaviour of its pure base metal Ti. The results showed that increasing azide concentration increases the rate of corrosion (i_corr) and shifts negatively the rest potential (E_f), as well as decreases the spontaneous thickening rates of the inner and outer layers constituting the passive oxide film on each sample. These effects are more accentuated for the alloy than for the metal. Moreover, the electrical resistance (R_ox) and the relative thickness (1/C_ox) of the oxide films on the two samples exhibit an almost linear decrease vs. NaN₃ concentration. The results suggested that addition of Al and V to Ti, although improves its machinability, yet it decreases the performance of its surface oxide film to protect the degradation of the metal. The alloy was found to be more susceptible to corrosion than its base metal, since Ti expresses higher apparent activation energy (E_a) for the corrosion process than Ti–6Al–4V. Electrochemical behaviour of Ti in azide medium was also compared with that in various halide solutions. It was found that Ti has a stronger propensity to form spontaneous passivating oxide layers in bromide more than in azide and other halide media, where the positive shift in the value of E_f and the simultaneous increase in the oxide film resistance (R_ox) follow the sequence: Br⁻ > > Cl⁻ > I⁻ > F⁻.     

Electrochemical study on hot corrosion of Si-modified aluminide coated In-738LC in Na2SO4-20 wt.% NaCl melt at 750 °C

The corrosion performance of the slurry Si-modified aluminide coating on the nickel base superalloy In-738LC exposed to low temperature hot corrosion condition has been investigated in Na₂SO₄-20 wt.% NaCl melt at 750 °C by combined use of the anodic polarization and characterization techniques.The coated specimen showed a passive behavior up to −0.460 V vs. Ag/AgCl (0.1 mol fraction) reference electrode, followed by a rapid increase in anodic current due to localized attack in the higher potential region. In the passive region, the anodic dissolution of constituents of the coating occurred through the passive film, probably SiO₂, at slow rate of 20-30 μA/cm². The passive current for the Si-modified coating was two orders of magnitude smaller than that for bare In-738LC, which is known as Cr₂O₃ former in this melt. This indicates that the SiO₂ film is chemically more stable than Cr₂O₃ film under this condition. However, pitting-like corrosion commenced around −0.460 V and proceeded at the high rate of 100 mA/cm² in the higher potential region than +0.400 V. The corrosion products formed on the coating polarized in different anodic potentials were characterized by SEM, EDS and XRD. It was found from the characterization that oxidation was dominant attack mode and no considerable sulfidation occurred at 750 °C. The SiO₂ oxide was not characterized in the passive region because the thickness of the passive film was extremely thin, but was detected as the primary oxide in the localized corrosion region, where the selective oxidation of Al was observed by further progress of the corrosion attack front into the inner layer of coating.     

Corrosion product analysis on crevice corroded Alloy-22 specimens

Surface analytical techniques were applied to characterize corrosion products formed during the crevice corrosion of the Ni–Cr–Mo(W) Alloy-22 in 5 mol/L NaCl at 120 °C. Micro-Raman spectroscopy demonstrated the formation of polymeric molybdates within the crevice corroded region where intergranular corrosion dominated. The location and chemical speciation of the Mo and W species formed was investigated by Raman mapping. Crevice corrosion was found to propagate preferentially across the alloy surface rather than to penetrate deeply at localized sites, a feature which appears to be linked to the formation and build-up of polymeric molybdates.     

Crevice corrosion damage function for grade-2 titanium of iron content 0.078 wt% at 95 °C

A crevice corrosion damage function has been developed for grade-2 titanium in 0.27 mol/dm³ NaCl at 95 °C. Crevice corrosion experiments were conducted for various durations using a galvanic coupling technique, and corrosion depth profiles subsequently measured using a combination of metallographic and image analysis techniques. The damage function was then determined by plotting the maximum penetration depth (d_max) in μm as a function of time (days). This function possessed two clear stages; an initial stage in which d_max = 89.4t^0.87, and a second stage in which corrosion spread laterally without an increase in d_max, before the crevice finally passivated. The initial high penetration rate was associated with an intergranular attack down Fe-containing grain boundaries. In the second stage, further increases in d_max were limited by the IR drop between the propagation sites deep within the grain boundaries and the external cathode.