Corrosion electrochemical characteristics of red iron oxide pigmented epoxy coatings on aluminum alloys

Red iron oxide pigmented epoxy coatings were prepared on aluminum alloys and were characterized by electrochemical impedance spectroscopy (EIS) immersed in NaCl solution. The evolutions of impedance models of coated metals were obtained by the fitting analysis of experimental data using suitable equivalent electrical circuits (EEC). The results indicated that the composite electrode system could be fitted by three impedance models. At the initial immersion stage, coatings acted as a barrier layer and only performed a simple circuit consisting of a coating resistance (R_c) parallel to a coating capacitance (C_c). After a certain time of exposure, water and (or) oxygen arrived at the metal surface through the coating, leading to the formation of electrochemical corrosion sites at metal interface and thereby the appearance of double-layer capacitance (C_dl) and charge transfer resistance (R_ct). After intensive attacking of metal substrates, the mass transfer of corrosion products was in difficulty. In this case, the diffusion elements were added to the EEC. It was found that due to the presence of inert pigment particles, the mass transfer behaviors were interestingly different from those of the varnish polymer coatings. Electrical parameters were also obtained from the EIS data. lnC_c-time curve showed a Case II water sorption kinetics, typical non-Fickian diffusion for water uptake.     

Corrosion Behavior of Thermally Sprayed NiCrBSi Coating on 16MnR Low-Alloy Steel in KOH Solution

NiCrBSi coatings were selected as protective material and air plasma-sprayed on 16MnR low-alloy steel substrates. Corrosion behavior of 16MnR substrates and NiCrBSi coatings in KOH solution were evaluated by polarization resistance (R _p), potentiodynamic polarization curves, electrochemical impedance spectroscopy, and immersion corrosion tests. Electrolytes were solutions with different KOH concentrations. NiCrBSi coating showed superior corrosion resistance in KOH solution compared with the 16MnR. Corrosion current density of 16MnR substrate was 1.7-13.0 times that of NiCrBSi coating in the given concentration of KOH solution. By contrast, R _p of NiCrBSi coating was 1.2-8.0 times that of the substrate, indicating that the corrosion rate of NiCrBSi coating was much lower than that of 16MnR substrate. Capacitance and total impedance value of NiCrBSi coating were much higher than those of 16MnR substrate in the same condition. This result indicates that corrosion resistance of NiCrBSi coating was better than that of 16MnR substrate, in accordance with polarization results. NiCrBSi coatings provided good protection for 16MnR substrate in KOH solution. Corrosion products were mainly Ni/Fe/Cr oxides.     

Automatic classification of polymer coating quality using artificial neural networks

Two artificial neural networks (ANN)—one for classification of polymer coating quality based on phase angle (Φ)-log frequency (f) data and one for classification based on log impedance modulus (/Z/)-log f data—have been trained using three sets of theoretical impedance spectra for polymer coated steel-spectra for good, intermediate and poor coating quality. The trained ANNs have been tested using experimental impedance spectra for six different polymer coating systems on steel collected during exposure at a remote marine test site for exposure periods up to one year. In general, excellent agreement between the predictions of coating quality made by experienced operators based on general features of the impedance spectra and parameters such as breakpoint frequency f_b and pore resistance R_po on the one hand and the classification results obtained from the ANNs on the other hand was obtained. Evaluation of the results of these analyses was made easier by introduction of the coating quality index (CQI) which has values between 0 and 1. Occasional discrepancies observed between classification results based on Φ-log f data vs. log /Z/-log f data occurred in the transition region between two types of classification, e.g. between intermediate and poor. These discrepancies have been explained based on the experimental data for R_po and f_b and their time dependence.     

Study on corrosive electrochemical behaviors of zinc‐rich and graphite‐filled epoxy coatings in 3.5 wt% NaCl solution

Environment behaviors and degradation mechanisms of two organic epoxy coatings coated on carbon steel sheets in 3.5 wt% NaCl neutral solution were studied by electrochemical impedance measurements and atomic force microscopy (AFM). The results showed that the coating resistance (R_p) of the graphite‐filled epoxy coating tested, which presents the film barrier performance, is higher than those of 6101 epoxy resin for initial seawater immersion, but the coating resistance of the zinc‐rich epoxy coating was lower than that of 6101 epoxy resin. After salt spray tests, zinc‐rich epoxy coating coated on the metal still has good anti‐corrosion performances due to the existence of protection effects called “electrochemical” and “chemical” protection. Those behaviors and degradation mechanisms of two coatings can be explained by a series of measured electrochemical impedance spectroscopy measurements, and two equivalent circuit models were proposed to explain the degradation processes of the two organic coatings.     

Electrochemical impedance study on galvanized steel corrosion under cyclic wet-dry conditions--influence of time of wetness

Electrochemical impedance technique has been applied to study the corrosion behavior of galvanized steel under wet-dry cyclic conditions with various drying periods. The wet-dry cycles were carried out for the period of 336 h by exposure to alternate conditions of 1 h immersion in a 0.5 M NaCl solution and drying for various time periods (11, 7 and 3 h) at 298 K and 60% RH. During the wet-dry cycles, the polarization resistance, R_p, and solution resistance, R_s, were continuously monitored. The instantaneous corrosion rate of the coating was estimated from the obtained R_p⁻¹ and time of wetness was determined from the R_s values. The corrosion potential, E_corr, was also measured only during the immersion period of each wet-dry cycle. In all cases, the corrosion was accelerated by the wet-dry cycles in the early stage, and started to decrease at a certain cycle and finally became similar to that at the initial cycle. The underlying steel corrosion commenced after the corrosion rate started to decrease. The shorter drying period in each cycle led to higher amount of corrosion of the coating because the surface was under wet conditions for longer periods. On the other hand, time to red rust appearance due to occurrence of the underlying steel corrosion became shorter as the drying period increased, although the total amount of corrosion was smaller. The corrosion mechanism of substrate steel under various drying conditions has been discussed, the galvanic coupling effect being taken into account.     

The corrosion protection of mild steel by polypyrrole/polyphenol multilayer coating

Electrochemical synthesis of very thin polyphenol (PPhe) film was achieved on polypyrrole coated mild steel electrode (MS/PPy) and a multilayer coating was obtained, cyclic voltammetry technique was used for the synthesis. The corrosion performance of this multilayer coating and single PPy coating were investigated in 0.05 M H₂SO₄ solution by using electrochemical impedance spectroscopy (EIS), anodic polarization curves and open circuit potential (E_ocp)-time curves were used. It was found that the multilayer coating could provide much better protection than the single PPy coating for corrosion of MS for much longer periods and an efficiency of 98.3% was determined for this coating after 340 h exposure time in corrosive medium. It is proposed that the very thin PPhe film coated on top of PPy coating lowered the porosity and improved the barrier effect of the coating significantly.     

Poly(m‐phenylenediamine)‐coated 316L SS: A promising material for bipolar plates in PEMFC environment

The applicability of conducting polymer coatings to enhance corrosion resistance of bipolar plates in proton exchange membrane fuel cells (PEMFC) is gaining greater significance as electrical conductivity is as important as corrosion resistance. Metaphenylenediamine (mPD) monomer was electropolymerized to poly(m‐phenylenediamine) (PmPD) conducting polymer over 316L SS and characterized by attenuated total reflectance infrared spectroscopy to confirm the formation of P mPD polymer. Scanning electron microscopy was used to study the surface morphology of the polymer. Open‐circuit potential, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization studies were conducted to assess the corrosion protection performance of the PmPD polymer coating in PEMFC environment. The charge‐transfer resistance measured from EIS for the coated substrates was higher than the uncoated substrate. Potentiodynamic polarization studies showed lower corrosion current density for the PmPD‐coated substrates. All the results proved that the PmPD‐coated substrates could exhibit enhanced corrosion resistance in PEMFC environment.     

Electrochemical methods study on corrosion of 5% Al–Zn alloy‐coated steel under thin electrolyte layers

The corrosion behavior of a 5% Al–Zn alloy (GF) coated steel was investigated under cyclic wet–dry condition using electrochemical techniques. The wet–dry cycle was conducted by exposure to alternate condition of 1 h immersion in seawater and 7 h drying at ambient temperature. The polarization resistance, R_p of the coating was monitored during the wet–dry cycles by two points AC impedance method and the corrosion potential, E_corr was measured only when the coating was immersed in seawater. Simultaneously, the electrochemical impedance spectroscopy (EIS) of the coating was obtained after it was immersed in different cycles of wet–dry condition. The results obtained by two points AC impedance method had good agreement with those achieved from EIS technique, which proved that the two points AC impedance method was correct and an effective method for atmospheric corrosion study. The monitoring results indicated that the corrosion rate of GF coating firstly increased, then decreased slowly with time, and at last reached a relative steady state with local corrosion under the cyclic wet–dry alternate condition.     

Effect of Si nanoparticles on the corrosion protection performance of organic coating on carbon steel in chloride environment

This work examines the effect of silicon (Si) nanoparticles on the corrosion protection performance of epoxy coating over carbon steel by Electrochemical Impedance Spectroscopy (EIS) and Transmission Electron Microscopy. The EIS was performed in a 0.1 M NaCl solution after a wet/dry cyclic corrosion and continuous immersion test. The addition of Si nanoparticles increased the film resistance (R_f) and the charge transfer resistance (R_ct) of the coated steel. The surface analysis showed that uniform and fine Si-Fe complex oxides layers were formed acting as barrier layers that enhanced the corrosion protection of the coated steel in the wet/dry cyclic corrosion test. The results of the EIS of the coated steel with Si nanoparticles suggested that Si nanoparticles play a beneficial role in enhancing the corrosion resistance of organic coated steel.     

Effect of electrolyte and monomer concentration on anticorrosive properties of poly(N-methylaniline) and poly(N-ethylaniline) coated mild steel

The electrosynthesis of poly(N-methylaniline) (PNMA) and poly(N-ethylaniline) (PNEA) coatings on mild steel in aqueous oxalic acid solutions was carried out by potentiodynamic synthesis technique. The effects of monomer and electrolyte concentrations on electrochemical growth of PNMA and PNEA coatings on mild steel substrates were investigated. Repassivation peak did not appear during electrosynthesis of PNMA and PNEA coatings from solutions containing 0.1 M monomer and 0.1 M electrolyte. The tests for corrosion protection of the polymer coated and uncoated mild steel substrates were done in 3% NaCl solutions by dc polarization and electrochemical impedance spectroscopy (EIS) techniques. Corrosion tests revealed that PNMA and PNEA coatings exhibited effective anti-corrosive properties. The acidity of the polymerization solution was found to influence the anticorrosive behavior of the polymer coating.     

Investigating accuracy of the Tafel extrapolation method in HCl solutions

This paper discusses the validity and accuracy of the Tafel extrapolation method for determining corrosion rates of carbon steel in 1, 2 and 3 M HCl solutions open to air. Corrosion rates obtained from polarization experiments were compared with that of weight loss method. For analysing data obtained from polarization experiments electrochemical impedance spectroscopy (EIS) measurements were performed before polarization experiments. The results showed that formation of a corrosion product film and increasing the polarization resistance (R_p) of this film with time cause the corrosion rates obtained from Tafel extrapolation tend to be higher than corrosion rates obtained from weight loss test.     

An evaluation of the electrochemical frequency modulation (EFM) technique

The EFM technique has been used to calculate anodic and cathodic Tafel slopes as well as corrosion current densities for the systems Cu/NaCl, Al 5083/NaCl, stainless steel/NaCl and mild steel in H₂SO₄ and NaCl. These values have been compared with those obtained from the analysis of polarization curves determined in the vicinity of the corrosion potential. In addition, polarization resistance values calculated based on the analysis of EFM data have been compared with values obtained from analysis of impedance data collected for the same systems. In most cases the corrosion rates determined with the EFM technique were much higher than the values determined with the other two techniques. This result is mainly due to the fact that for systems with low corrosion rates the modulation frequencies that are used in the EFM technique are in the capacitive region of the impedance spectra. Good agreement of corrosion rates obtained with the EFM and the polarization techniques was only observed for the mild steel/H₂SO₄ system that has very high corrosion rates. Analysis of EFM data assuming charge transfer or diffusion control produced different Tafel slopes and corrosion rates, but the same polarization resistance (R_p) values. When the EFM technique was applied to a resistor, the calculated R_p value equaled the value of the resistance which is further proof that the EFM technique measures the impedance of a corroding system in a narrow frequency band. The difference to the traditional EIS technique is that the amplitude of the ac signal can be different at different frequencies.     

The effects of sulfate reducing bacteria on corrosion of carbon steel Q235 under simulated disbonded coating by using electrochemical impedance spectroscopy

The effect of sulfate reducing bacteria (SRB) on the corrosion of the carbon steel Q235 has been investigated in the crevice under the simulated disbonded coating in the soil-extract solutions (SES). The results of electrochemical impedance spectroscopy (EIS) show that the corrosion rate is inhibited in the SES with SRB during the stationary phase of SRB, but enhanced during the death phase. The comparison of the polarization (R_p) and the charge transfer resistances (R_t) has indicated that the biofilm seriously influences the reactive procedure of metal/solution interface. SRB is found in the pits on the surface of the steel.     

Characterization and Performance of Magnetron-Sputtered Zirconium Coatings Deposited on 9Cr-1Mo Steel

Zirconium coatings of different thicknesses have been deposited at 773 K on 9Cr-1Mo steel substrate using pulsed DC magnetron sputtering. These coatings were heat treated in vacuum at two different temperatures (1173 and 1273 K) for one hour. X-ray diffraction (XRD) analysis of Zr-coated samples revealed the formation of α-phase (HCP structure) of Zr. XRD analysis of heat-treated samples show the presence of Zr₃Fe and Zr₂Fe intermetallics. The lattice parameter of these coatings was calculated, and it matches with the bulk values when the thickness reached 2µm. In order to understand this, crystallite size and strain values of these coatings were calculated from XRD plots employing Williamson-Hall method. In order to assess the performance of the coatings, systematic corrosion tests were carried out. The corrosion current density calculated from the polarization behavior showed that the corrosion current density of the uncoated 9Cr-1Mo steel was higher than the coated sample before and after the heat treatment. Studies using electrochemical impedance spectroscopy confirmed that the coated steel has higher impedance than the uncoated steel. The corrosion resistance of 9Cr1Mo steel had improved after Zr coating. However, the corrosion resistance of the coating after heat treatment decreased when compared to the as-deposited coating. The microstructure and composition of the surface oxide film influence the corrosion resistance of the Zr-coated 9Cr1Mo steel.     

An electrochemical impedance spectroscopy study of the corrosion behaviour of PVD coated steels in 0.5 N NaCl aqueous solution: Part II.: EIS interpretation of corrosion behaviour

In Part I, of this work the equivalent circuits for electrochemical impedance spectroscopy (EIS) modelling of PVD coated steels in 0.5 N NaCl solution were established. In this paper, Part II, the EIS spectra of such coated systems are modelled using the equivalent circuits. The circuit parameters obtained are correlated with the dielectric characteristics, and microstructure of steels and PVD hard coatings. Coating porosity and localised corrosion with exposure time have also been determined using the corrosion potential difference (ΔE_corr) between mild steel and PVD coatings and polarisation resistance R_p, which was obtained through EIS modelling using equivalent circuits. In addition, diffusion rates of the reactants (e.g. oxygen) through ‘permeable’ defects (e.g. pores) are studied by introducing the diffusion impedances W and O in EIS modelling. It has been found that the usage of impedances W and O is closely related to the crystallite features of PVD coatings. Warburg impedance (W) is most suitable for columnar crystallites, while the co-tangent-hyperbolic diffusion impedance (O) is best for the equiaxed crystallite structure. Finally, visual inspection, SEM examination, and the scanning reference electrode technique were employed to observe the corrosion progress of PVD coated steels with immersion time, in order to validate the EIS interpretation.     

Evaluation of localized corrosion phenomena with electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ANA)

The use of electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA) for non-destructive evaluation of corrosion processes is illustrated for three model systems. EIS can be used to detect and monitor localized corrosion of Al alloys and determine pit growth laws which can be used for lifetime prediction purposes. Electrochemical potential and current noise data can be analyzed in the time and the frequency domain. A comparison of noise data obtained for Pt and an Al 2009/SiC metal matrix composite (MMC) exposed to 0.5 N NaCl has shown that the use of potential noise data alone can lead to erroneous conclusions concerning corrosion kinetics and mechanisms. The electrochemical noise data have been evaluated using power spectral density (PSD) plots in an attempt to obtain mechanistic information. The system Fe/NaCl has been used to determine the relationship between the polarization resistance R_p obtained from EIS data and the noise resistance R_n determined by statistical analysis of potential and current noise data. Potential and current noise can be recorded simultaneously allowing construction of noise spectra from which the spectral noise resistance R can be obtained as the limit for zero frequency. Good agreement between R_P, R_n and R has been observed for iron exposed to NaCl solutions of different corrosivity. For polymer coated steel exposed to 0.5 N NaCl for five months analysis of EIS data allows to draw conclusions concerning the degree of disbonding of the coating and the decrease of the coating resistivity with exposure time. R_n and R obtained from electrochemical noise data for an alkyd coating on cold rolled steel agree with each other and show the same time dependence as R_p and the pore resistance R_po determined from EIS data, but are significantly lower than R_p and R_po. The relationships of derived noise parameters such as R_n and R to coating properties and to the remaining lifetime of a polymer coating are not clear at present.     

Electrochemical Behavior and Stress Corrosion Sensitivity of X70 Steel Under Disbonded Coatings in Korla Soil Solution

The corrosion of X70 pipeline steel under a model disbonded coating was studied in a simulated solution of Korla soil by combining in situ electrochemical measurements at different locations in the crevice and stress corrosion cracking (SCC) sensitivity analyses in the corresponding simulated environments. The results from electrochemical impedance spectroscopy showed that the corrosion product resistance R _t and charge transfer resistance R _ct of X70 steel first increased and then decreased with increasing distance from the opening of the crevice in the disbonded coating. Scanning electron micrographs showed that pitting in the crevice became more severe at deeper locations in the crevice. Slow strain rate tests showed that the lowest SCC sensitivity of X70 steel was found at 15 cm away from the opening, and the highest SCC sensitivity was at the end of the crevice.     

Effect of nanoparticles on the anticorrosion and mechanical properties of epoxy coating

Homogeneous epoxy coatings containing nanoparticles of SiO₂, Zn, Fe₂O₃ and halloysite clay were successfully synthesized on steel substrates by room-temperature curing of a fully mixed epoxy slurry diluted by acetone. The surface morphology and mechanical properties of these coatings were characterized by scanning electron microscopy and atomic force microscopy, respectively. The effect of incorporating various nanoparticles on the corrosion resistance of epoxy-coated steel was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy. The electrochemical monitoring of the coated steel over 28 days of immersion in both 0.3 wt.% and 3 wt.% NaCl solutions suggested the beneficial role of nanoparticles in significantly improving the corrosion resistance of the coated steel, with the Fe₂O₃ and halloysite clay nanoparticles being the best. The SiO₂ nanoparticles were found to significantly improve the microstructure of the coating matrix and thus enhanced both the anticorrosive performance and Young's modulus of the epoxy coating. In addition to enhancing the coating barrier performance, at least another mechanism was at work to account for the role of the nanoparticles in improving the anticorrosive performance of these epoxy coatings.     

EIS study of the corrosion behaviour of zinc-based coatings on steel in quiescent 3% NaCl solution. Part 2: coatings covered with an inhibitor-containing lacquer

An EIS study has been made of the behaviour of several lacquered and inhibited zinc-based coatings on steel exposed to a 3% NaCl solution in quiescent conditions. Under the hypothesis that the HF-LF arc supplied the R_t value of the corrosion reaction, the possibility of obtaining quantitative information about the effect of the lacquer film and the inhibitor on the progress of attack has been demonstrated. Different values of the constant B in the Stern-Geary equation must be used depending on the specific metallic coating tested. The relatively high interfacial capacitance values of the lacquered coating suggest a highly defective lacquer film which leave a considerable fraction of the surface of the metallic substrate exposed to the corrosive medium.     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.