On the corrosion resistance of porous electroplated zinc coatings in different corrosive media

The corrosion resistance of an electroplated (EP) Zn coating whose surface was chemically etched to produce surface defects (pores) is investigated in this work. Impedance and DC polarisation measurements were employed to study the behaviour of such coating in various corrosive media (NaCl, NaOH and rain water). Four different faradaic relaxation processes were clearly revealed in different NaCl concentrations (from 0.1 to 1 M). In the most concentrated solutions at least three relaxation processes at low frequencies (LF) appeared and were related to zinc deposition and dissolution. At lower concentrations and depending on the pH, only one process was observed. The charge transfer resistance (R_ct) and the corrosion current (I_corr) were practically stable in the pH range 5-10. In deaerated NaCl 0.1 M, the EIS diagrams showed two time constants at very close frequencies. From the EIS diagrams the porous nature of the coating was highlighted and showed that the dissolution mechanisms occurred at the base of the pores.     

EIS monitoring study of atmospheric corrosion under variable relative humidity

Electrochemical impedance spectroscopy (EIS) technique was used to investigate atmospheric corrosion in laboratory simulated environments with variable relative humidity (RH) and fixed Cl⁻ content. The results show the suitability of EIS for analyzing electrochemical corrosion behaviour at 5-100% RH. At 5-30% RH, EIS spectra reflected the character of the electrode, whereas at 40-100% RH, the model of EIS spectra was established with the help of surface analysis. From 70% RH, the film resistance (R_r) reflects the degree of corrosion and the charge transfer resistance (R_t) provides quantitative representation of the corrosion rate, which were verified by weight loss tests.     

Evolution of dissolution processes at the interface of carbon steel corroding in a CO2 environment studied by EIS

The evolution of interfacial phenomena during CO₂ corrosion of C1018 carbon steel was characterized by EIS (Electrochemical Spectroscopy Impedance) and LPR (Linear Polarization Resistance). Turbulent conditions were simulated by a channel flow cell with deoxygenated 3 wt.% NaCl solution at 80 °C and pH 6 during 158 h. EIS helped in the characterization of the dynamic mechanism during the formation of the unprotective porous Fe₃C layer, and subsequent precipitation of the protective FeCO₃ layer inside the cementite. The experimental response of the active states at the interface was characterized by electrical passive elements with constant phase parameter analogs showing good agreement with the experimental results.     

Initial corrosion protection of Zn–Mn alloys electrodeposited from alkaline solution

The effects of a deposition current density (c.d.) on the corrosion behaviour of Zn–Mn alloy coatings, deposited from alkaline pyrophosphate solution, were investigated by atomic absorption spectrophotometry (AAS), X-ray diffraction (XRD), atomic force microscopy (AFM), optical microscopy, electrochemical impedance spectroscopy (EIS) and measurement of corrosion potential (E_corr). XRD analysis disclosed that zinc hydroxide chloride was the main corrosion product on Zn–Mn coatings immersed in 0.5 mol dm⁻³ NaCl solution. EIS investigations revealed that less porous protective layer was produced on the alloy coating deposited at c.d. of 30 mA cm⁻² as compared to that deposited at 80 mA cm⁻².     

Corrosion mechanisms of steel concrete moulds in contact with a demoulding agent studied by EIS and XPS

The behaviour of E24 mild steel was studied by XPS analysis and electrochemical impedance spectroscopy (EIS) in a filtered solution of cement (pH 13), and an alkyl N-aminodiphosphonate aqueous solution called Aquadem^® (7?pH?13). XPS results showed that the corrosion products developed in both media consisted of Fe₂O₃, covered by a very thin layer of goethite. The thickness of this oxide layer was estimated to be 3 nm. XPS analysis also demonstrated the adsorption of Aquadem^® on the outer layer of FeOOH for pH lower than the zero charge pH of goethite (7.55). From XPS and EIS results, physical models of the E24 steel/electrolyte interface are proposed as a function of pH. For 11?pH?13, the steel is covered by a passive film, while for pH?10, pitting corrosion takes place. At pH 7, an additional mass transport phenomenon must be taken into account. The fitting procedure provided values for several physical parameters (electrolyte resistance, passive film resistance), from which the film capacitance and the dielectric constant of the oxide layer were calculated.     

Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater

The corrosion behavior of the 70/30 Cu-Ni alloy in stagnant, aerated pristine and sulfide-containing simulated seawater as a function of exposure time was investigated with polarization curve measurement and electrochemical impedance spectroscopy (EIS). It was demonstrated that the compact protective oxide film formed on the 70/30 Cu-Ni alloy resulted in the decrease of corrosion rate in aerated pristine seawater; while the corrosion rate of 70/30 Cu-Ni alloy in aerated sulfide-containing seawater increased dramatically due to the catalysis of the sulfide ions or sulfide scale for both the cathodic and anodic reactions. The impedance spectra and the corresponding equivalent circuits confirmed that a duplex layer of a surface film was formed on the 70/30 Cu-Ni alloy in aerated pristine seawater after a period of time and that the inner layer was responsible for the good resistance of the alloy; while only a porous and non-protective corrosion product layer formed on the 70/30 Cu-Ni alloy in aerated sulfide-containing seawater, which made small values of charge transfer resistance (R_ct) to last for a abnormally long time by interfering with the growth of the protective oxide film. The composition of the surface film on the alloy in pristine and sulfide-containing seawater for different exposure times were investigated thoroughly by XPS. It was found that the duplex corrosion product layer formed on the alloy in pristine seawater was composed of an inner Cu₂O and an outer CuO layer. The porous and non-protective corrosion product layer formed on the alloy in aerated sulfide-containing seawater was a mixture of CuCl, Cu₂S, NiS, Cu₂O and NiO with trace amounts of CuO and Ni(OH)₂ and that the most significant component was Cu₂S. In addition, SEM was used to analyze the topography of the 70/30 Cu-Ni alloy in both solutions after different exposure times.     

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

Effects of corrosion product deposit on the subsequent cathodic and anodic reactions of X-70 steel in near-neutral pH solution

The effects of corrosion product deposit on the subsequent anodic and cathodic reactions of X-70 steel in a near-neutral pH solution were investigated by localized electrochemical impedance spectroscopy (LEIS), scanning vibrating micro-electrode (SVME) and macroscopic EIS measurements as well as surface analysis technique. It is found that the deposit layer formed on the steel surface is porous, non-compact in nature. The presence of a corrosion product layer would enhance adsorption, but significantly inhibit absorption and permeation of hydrogen atoms into steel. It is due to the porous structure of the deposit that generates a spatial separation of cathodic and anodic reaction sites, resulting in an increased effective surface area for hydrogen adsorption and, simultaneously, a “blocking” effect on hydrogen absorption and permeation. The deposit enhances greatly anodic dissolution of the steel, which is attributed to the adsorption of the intermediate species and the resultant “self-catalytic” mechanism for corrosion of the steel in near-neutral pH solution. In the presence of corrosion product deposit on the pipeline steel surface, pipeline corrosion, especially pitting corrosion, is expected to be enhanced. Stress corrosion cracks could initiate from the corrosion pits that form under deposit. However, deposit does not contribute to hydrogen permeation, although the hydrogen evolution is enhanced.     

Microbially influenced corrosion of zinc and aluminium - Two-year subjection to influence of Aspergillus niger

Aspergillus niger. Tiegh., a filamentous ascomycete fungus, was isolated from the metal samples exposed to marine, rural and urban sites in Lithuania. Al and Zn samples were subjected to two-year influence of A. niger under laboratory conditions in humid atmosphere. Electrochemical impedance spectroscopy (EIS) ascertained microbially influenced corrosion acceleration (MICA) of Zn and inhibition (MICI) of Al. EIS data indicated a two-layer structure of corrosion products on Zn. The microorganisms reduced the thickness of the inner layer, whose passivating capacity was much higher when compared to that of the outer layer. An increase in aluminium oxide layer resistance but decrease in the layer thickness implied that MICI affected primarily the sites of localized corrosion of Al (pores, micro-cracks, etc.). X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) studies indicated that bioproducts (i.e. organic acids) did not form crystalline phases with corrosion products of zinc. The study suggested a hypothesis that microorganisms could be used as corrosion protectors instead of toxic chemicals, application of which tends to be increasingly restricted.     

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 of ultra-high-purity Mg in 3.5% NaCl solution saturated with Mg(OH)2

Corrosion was evaluated for ultra-high-purity magnesium (Mg) immersed in 3.5% NaCl solution saturated with Mg(OH)₂. The intrinsic corrosion rate measured with weight loss, P_W = 0.25 ± 0.07 mm y⁻¹, was slightly smaller than that for high-purity Mg. Some specimens had somewhat higher corrosion rates attributed to localised corrosion. The average corrosion rate measured from hydrogen evolution, P_AH, was lower than that measured with weight loss, P_W, attributed to dissolution of some hydrogen in the Mg specimen. The amount of dissolution under electrochemical control was a small amount of the total dissolution. A new hydride dissolution mechanism is suggested.     

Corrosion and surface study of sputtered Al–W coatings with a range of tungsten contents

The corrosion behaviour of sputter-deposited, Al–W coatings with three different concentrations of tungsten (0.6, 3.5 and 11 at.% W) on AA7075 aluminium alloy substrates was investigated in chloride media using EIS, salt-fog tests and surface analyses. The surface analyses were performed with XPS/AES, SEM/EDS and TEM microscopy. The presence of W reduces the thickness of the oxide layer formed after the EIS test, as proved by the compositional depth profile. From the EIS data of the investigated Al–W_x coatings, the polarisation resistance (R_p) and the capacitive behaviour as a function of the immersion time were obtained. A small increase in R_p suggested improved corrosion properties over time. However, the extent of the improvement depends on the content of W and the coating-surface morphology (the presence of growth defects on the coating surface). The capacitive behaviour observed at high frequencies was related to the dielectric properties and the thickness of the barrier oxide film formed. The salt-fog tests to some extent supported the results from the EIS measurements. However, there was a difference between the corrosion EIS and salt-fog test results in the case of the Al₈₉W₁₁ coatings. The thickest oxide layer and the “layering” into the three regions (porous, semi-porous and intact) were observed when the salt-fog corrosion test was performed on the Al₈₉W₁₁ coating. Galvanic corrosion, probably due to the local compositional and structural inhomogeneities, takes place. However, this was not unambiguously observed during the EIS corrosion test.     

Inhibitory effect of some amino acids on corrosion of Pb-Ca-Sn alloy in sulfuric acid solution

The present article describes the inhibition effect of amino acids cysteine (Cys), methionine (Met) and alanine (Ala), towards the corrosion of lead-alloy (Pb-Ca-Sn) in H₂SO₄ solution by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), weight loss measurement and scanning electron microscopy (SEM) methods. The influence of inhibitor concentration, temperature and time on inhibitory behavior of the amino acids was investigated. The corrosion data including corrosion current density (I_corr), corrosion potential (E_corr) and charge transfer resistance (R_ct) were determined from Tafel plots and EIS. Recording impedance spectra showed that the charge transfer resistance is increased by increasing adsorption time. The SEM micrographs revealed that the corroded surface area is decreased in the presence of amino acids. Meanwhile, the inhibition efficiency (IE) was found to be depending on the type of amino acid and its concentration. The IE for 0.1 M Cys in 0.5 M H₂SO₄ is greater than 96%. Adsorption isotherms were fitted by Langmuir isotherm.     

The electrochemical impedance response of film-covered mild steel in neutral aerated solutions

Electrochemical Impedance Spectroscopy (EIS) has been widely used in the study of corrosion processes and data interpretation is often via simple equivalent circuits. However, such circuits often can not be used to model real EIS data obtained with film covered or corroded steel electrodes in near-neutral solutions, especially when interrelation between the various components of the equivalent circuit is allowed for. Electrochemical impedance spectra have been obtained at the corrosion potential for a mild steel rotating disc electrode (RDE) in chloride solutions with addition of zinc-polyphosphate inhibitor, which show clear evidence of mass transport through a porous layer. In addition, d.c. measurements show very low values of the steady state diffusion current, a significant effect of rotation speed of the RDE on the anodic reaction and evidence that the layer properties depend on the stirring conditions. Analysis of the impedance spectra with a general model previously proposed provides evidence that due to film-limited mass transfer the anodic reaction becomes reversible.     

Surface characterization of oxides grown on the Ti–13Nb–13Zr alloy and their corrosion protection

Oxide films were formed on the biocompatible alloy Ti–13Nb–13Zr in a phosphate buffer at open-circuit potential (E_oc), potentiodynamically up to 8 V, or by micro-arc oxidation (MAO) at 300 V. Their electrochemical properties were assessed in a phosphate buffer saline solution (PBS). EIS and SEM results showed that the E_oc and potentiodynamically formed oxide films were compact and behave as a monolayer, while the MAO oxide was a bilayered film (compact inner and porous outer layers). Open-circuit potential and EIS resistance values indicated that the MAO oxide provides the best corrosion protection for the alloy in PBS.     

SRB-biofilm influence in active corrosion sites formed at the steel-electrolyte interface when exposed to artificial seawater conditions

Electrochemical evolution of the interface formed by carbon steel exposed to artificial seawater with nutrients in the presence and absence of mixed cultures that contain sulfate-reducing bacteria (SRB) is characterized by electrochemical impedance spectroscopy (EIS). The artificial seawater in sterile conditions progressively covered the surface of the steel sample with two different layers after 30 days of exposure. An outer layer is formed by a mixture of chlorides and phosphorus-based iron corrosion products with organic compounds from the culture media, and an inner layer is formed by corrosion products mixture constituted mainly by phosphorus-base products. Alternatively, under biotic conditions there was one heterogeneous layer composed by a mixture of phosphorous and sulfur-based corrosion products and biofilm. Three time constants were observed with EIS for sterile conditions. At low frequencies one constant is associated with the charge transfer resistance related to the iron dissolution reaction and inversely proportional to the active area; the porous resistance magnitudes at medium frequencies characterized the physicochemical properties of the inner layer, and high frequency described the electrical properties of the outer mixture layer. Low carbon steel in the presence of SRB (halophilic hydrogenotrophic) showed the impedance distribution after the formation of a corrosion product thick black layer mixed with organic composites and bio-entities. The SRB-biofilm enhanced the corrosion rate and influenced the appearance of diffusion controlled mechanism process. Electrical passive analogs in terms of constant phase elements characterized the evolution of the cover films formed and the impedance of the layers with time. The mechanisms are characterized based on the impedance response for three time constants in the absence of SRB and one time constant with a finite Warburg element when SRB are present in the electrolyte. The validation of the theoretical approximation with electrical analogs was in good agreement with the experimental results.     

Electrochemical behaviour of Ni-base alloys exposed under oil/gas field environments

The electrochemical behaviour of Ni-base alloys (Inconel 625, Inconel 718, G3 and Incoloy 825) is carried out at 80 °C in CO₂/H₂S corrosion environments using cyclic potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. The passivity mechanisms are analysed and discussed. In addition, some significant characterisation parameters such as E_corr, I_pass, E_pit, E_pp, ΔE and I_pass in cyclic polarisation curves are analysed and compared to reveal the corrosion resistance of various Ni-base alloys. The equivalent circuit model and ZsimpWin software are utilised to discuss the Nyquist plots of various Ni-base alloys. The diffusion mechanism in EIS measurement is discussed. The result shows that the corrosion resistance of the Ni-base alloys to CO₂ corrosion or CO₂/H₂S corrosion follows the sequence: Inconel 625 > G3 > Inconel 718 > Incoloy 825. H₂S works as a cathodic depolariser with accelerating initiation of the corrosion process.     

Corrosion relationships as a function of time and surface roughness on a structural AE44 magnesium alloy

Pit initiation, growth, and coalescence corrosion mechanisms of an AE44 magnesium alloy subjected to a salt-water environment were quantified. Stereological quantities were evaluated using optical microscopy, scanning electron microscopy, and laser beam profilometry. Three corrosion mechanisms clearly arose: pitting, intergranular, and general. Pitting began as the result of localized galvanic dissolution between the intermetallics and magnesium matrix. Intergranular corrosion arose as pits coalesced. General corrosion arose by dissolution and regeneration of a Mg(OH)₂ film at a continuous rate. Stereological quantification demonstrated that the corrosion pit number density and pit radius size distribution initially increased before decreasing due to pit coalescence.     

Corrosion inhibition by anionic surfactants of AA2198 Li-containing aluminium alloy in chloride solutions

This paper evaluates the inhibiting action of some anionic surfactants towards AA2198 corrosion in NaCl solutions; the effect of surfactant concentration in relation to chloride amount was determined.On separate electrodes, polarization curves were recorded after 1, 24 and 168 h immersion in the aggressive media, while EIS technique continuously monitored the alloy corrosion process.In general, these substances stifled both the cathodic and anodic processes and noticeably shifted the pitting potential (breakdown potential, E_BR) in the positive direction. The most efficient compounds were N-lauroylsarcosine sodium salt and sodium dodecyl-benzenesulfonate, able to withstand the effects of 0.1 M Cl⁻.     

Effect of Different Degrees of Sensitization on the EIS Response of 316L and 316 SS in Transpassive Region

Different heat treatments were conducted on 316L and 316 stainless steels, and the sensitized specimens were characterized using anodic polarization and EIS tests in 0.5 M H₂SO₄ containing 0.01 molar KSCN. The potential ranges related to the transpassive region related to each specimen were determined. The EIS experiments were conducted at different potentials in that region, and the results showed the presence of three different regions, namely the anodic dissolution of the passive layer, dissolution of the grain boundaries, and the occurrence of pitting corrosion owing to the variations in the anodic potential. The higher the applied sensitization temperature, the lower the obtained charge-transfer resistance (R _ct) values, but healing effect was observed at the temperatures above 600 °C for these alloys.