Atmospheric corrosion of zinc induced by runoff

Atmospheric corrosion and runoff of zinc were investigated during two years in humid tropical climate on hot dip galvanized steel and zinc samples. The high zinc mass loss (14.70 g m⁻²) is induced by the intensive zinc release (12.40 g m⁻²). No corrosion phase containing chloride was detected on the zinc surface, while a variety of sulfates not dissolved by rains reveals the sensitivity of zinc to SO₂ pollutant. However, two chloride-containing corrosion products were detected on the galvanized steel. Exponential equation is proposed that fits well the experimental data for zinc mass loss induced by runoff process as a function of the time of wetness. The formula gives possibility to predict the mass loss even before a steady state in the corrosion process has been reached. This equation can converge to a Benarie lineal function (C = At_w), when the coefficient b = 1 for the corrosion which is accelerated with the partial removal of the corrosion layer during the runoff phenomena.     

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

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

Biocorrosion of carbon steel alloys by an hydrogenotrophic sulfate-reducing bacterium Desulfovibrio capillatus isolated from a Mexican oil field separator

The hydrogenotrophic sulfate-reducing bacterium (SRB) Desulfovibrio capillatus (DSM14982^T) was isolated from an oil field separator with serious corrosion problems; this is the study of its role in the corrosion of carbon steels under anaerobic conditions. Immersion tests with two steel alloys, St-35.8 (typical carbon steel employed in European naval industry), and API-5XL52 (weathering alloy steel employed in Mexican oil industries) were performed. Total exposure was 45 days and different concentrations of thiosulfate as electron acceptor for bacterial growth were employed. The samples immersed in media with SRB undergo fast activation and numerous active sites form on the surface. Microscopic observations were made by environmental scanning electron microscopy (ESEM). Weight loss and electrochemical testing included open circuit potential (E_corr), polarization resistance (R_p), electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were measured with and without bacteria in the culture medium in order to determine corrosion rates and mechanisms. All electrochemical techniques have shown that after the end of the exponential phase the corrosion activity notably increased due to the high concentration of bacterial metabolites. Finally, the corrosion behavior of API-5XL52 was worse than St-35.8.     

Electrochemical behaviour and structure of rust formed on Si- and Al-bearing steel after atmospheric exposure

The corrosion resistance of Si- and Al-bearing steel was estimated by atmospheric exposure test, and the structure of the rust was examined by EPMA (electroprobe X-ray microanalysis) and TEM (transmission electron microscopy) analysis. Moreover, the electrochemical behaviour of rust was investigated by EIS (electrochemical impedance spectroscopy).The Si- and Al-bearing steel exhibited excellent corrosion resistance in the exposure test as compared with carbon steel (SM). EPMA and TEM analysis showed that Si and Al mainly existed in nanoscale iron complex oxides in the inner rust formed on this steel. The Al K spectrum of the rust exhibited a peak that was the same as that of Al₂O₃ in the EPMA and TEM-EELS (electron energy loss spectroscopy) analysis. This result suggests that Al was present in the complex oxides as Al³⁺. In the same way, Si was identified as being in an intermediate state in the complex oxides of the inner rust.EIS measurement of the exposure test samples revealed much higher rust resistance (R_rust) and corrosion reaction resistance (R_t) of Si- and Al-bearing steel compared to that of SM. Finally, it was found that nanoscale complex iron oxides formed in the inner rust of Si- and Al-bearing steel, resulting in increased R_rust and R_t, and corrosion suppression.     

Microbiologically influenced corrosion of X60 carbon steel in CO2‐saturated oilfield flooding water

The corrosion behavior of X60 carbon steel in CO₂‐saturated oilfield flooding water inoculated with sulfate‐reducing bacteria (SRB) was investigated using polarization curves and electrochemical impedance spectroscopy (EIS). With the propagation of SRB in the flooding water, the pH values of flooding water increased quickly in the initial 2 days and remained relatively steady during the later stage. Polarization curves showed that the corrosion current density decreased during the first 10 days due to the protection of corrosion products and SRB‐biofilms, and then increased possibly due to the partial detachment of the corrosion products and the biofilms. EIS analysis also showed that the charge transfer resistance increased initially and then decreased with exposure time. In the beginning of corrosion, the anodic dissolution of X60 steel was dominated by CO₂. After the formation of SRB‐biofilms, part of FeCO₃ corrosion products was converted to incompact FeS precipitates by SRB bio‐mineralization. Thus, the dispersed iron sulfide in SRB‐biofilms and X60 steel base may constitute a galvanic couple, accelerating the localized corrosion of the steel base in the flooding water.     

Erosion-corrosion behavior of nano-particle-reinforced Ni matrix composite alloying layer by duplex surface treatment in aqueous slurry environment

The present study concerns a duplex surface treatment of AISI 316L stainless steel to enhance the erosion-corrosion resistance. The duplex surface treatment consisted of Ni/nano-SiC and Ni/nano-SiO₂ predeposited by brush plating and a subsequent surface alloying with Ni-Cr-Mo-Cu by double glow process of the substrate. Results showed that under alloying temperature (1000 °C) condition, the amorphous nano-SiO₂ particles still kept the amorphous structure, whereas the nano-SiC particles had been completely decomposed and Ni, Cr reacted with SiC to form Cr_6.5Ni_2.5Si and Cr₂₃C₆. The electrochemical corrosion behaviors of composite alloying layers compared with the single alloying layer and 316L stainless steel were measured under a range of hydrodynamic conditions by recording the current response, open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Results showed that the increase of the impact velocity had significant influence on the current density of composite alloying layer with brush plating Ni/nano-SiC particles interlayer obtained under flowing condition at a potential of 200 mV, whereas there were only small fluctuations occurred at current response of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The results of potentiodynamic polarization indicated that, with increasing impact velocity under slurry flow conditions, the corrosion potentials of test materials decreased and the corrosion current densities of test materials increased. The corrosion resistance of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer was prominently superior to that of single alloying layer under slurry flow conditions; the corrosion resistance of composite alloying layer with brush plating Ni/nano-SiC particles interlayer was evidently lower than that of single alloying layer, but higher than that of 316L stainless steel under slurry flow conditions. The results of EIS indicated that, with respect to the R_tot obtained in sand-free flow, the impacts of sand particles dramatically decreased the R_tot values of composite alloying layer with brush plating Ni/nano-SiC particles interlayer, single alloying layer and 316L stainless steel, whereas the impact action slightly decreased that of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The weight loss rate studies suggested that the highly dispersive nano-SiO₂ particles were helpful to improve the erosion-corrosion resistance of composite alloying layer, whereas the carbides and silicide phase were deleterious to that of composite alloying layer due to the fact that preferential removal of matrix around the precipitated phase takes place by the chemical attack of aggressive medium.     

Corrosion behavior of SRB Desulfobulbus propionicus isolated from an Indian petroleum refinery on mild steel

In this study, Desulfobulbus propionicus (D. propionicus), a sulfate reducing bacterium (SRB) was isolated and identified in cooling towers by molecular biologic techniques. This bacterial species has been reported for the first time in the cooling towers of an Indian petroleum refinery. Corrosion behaviors were analyzed by electrochemical and weight loss methods. The high corrosion rate and the enhancement of anodic current in increased chloride environment was noticed in the presence of D. propionicus indicating that this SRB species enhances the pitting corrosion of mild steel. Propionate metabolism in H₂S production is discussed as a new pathway of corrosion enhancement.     

Effect of Geobacter sulfurreducens on the microbial corrosion of mild steel, ferritic and austenitic stainless steels

The influence of Geobacter sulfurreducens was tested on the anaerobic corrosion of four different steels: mild steel 1145, ferritic steel 403 and austenitic steels 304L and 316L. Within a few hours, the presence of cells induced a free potential (E_oc) ennoblement around +0.3 V on 1145 mild steel, 403 ferritic steel and 304L austenitic steels and slightly less on 316L. The kinetics of E_oc ennoblement depended on the amount of bacteria in the inoculum, but the final potential value depended essentially on the nature of the material. This effect was due to the capacity of G. sulfurreducens to create a direct cathodic reaction on steel surfaces, extracting the electrons directly from material. The presence of bacterial cells modified the corrosion features of mild steel and ferritic steel, so that corrosion attacks were gathered in determined zones of the surface. Local corrosion was significantly enhanced on ferritic steel. Potential ennoblement was not sufficient to induce corrosion on austenitic steels. In contrast G. sulfurreducens delayed the occurrence of pitting on 304L steel because of its capability to oxidize acetate at high potential values. The electrochemical behaviour of 304L steel was not affected by the concentration of soluble electron donor (acetate, 1–10 mM) or the amount of planktonic cells; it was directly linked to the biofilm coverage. After polarization pitting curves had been recorded, microscopic observations showed that pits propagated only in the surface zones where cell settlement was the densest. The study evidenced that Geobacter sulfurreducens can control the electrochemical behaviour of steels in complex ways that can lead to severe corrosion. As Geobacteraceae are ubiquitous species in sediments and soils they should now be considered as possible crucial actors in the microbial corrosion of buried equipment.     

Microbial corrosion of galvanized steel by a freshwater strain of sulphate reducing bacteria (Desulfovibrio sp.)

Microbially influenced corrosion of galvanized steel was investigated exposing coupons (2.0 × 2.0 cm) to culture of sulphate reducing bacteria strain Desulfovibrio sp. The coupons were exposed to the SRB culture for 4, 8, 24, 72, 96, 168, 360 and 744 h along with a control set in uninoculated medium. The results from the present study suggest that SRB were responsible for the corrosion of the galvanized steel. The corrosion rate of galvanized steel was not be correlated with the number of sessile SRB cells. Also Desulfovibrio sp. had an ability to produce EPS (Extracellular Polimeric Substances) and biodegrade the carbohydrate, that is the predominant component of the EPS produced by them. When Desulfovibrio sp. cells were in logarithmic phase, the concentration of dissolved zinc in the bulk solution was very toxic for Desulfovibrio desulfuricans.     

Microbial corrosion of galvanized steel in a simulated recirculating cooling tower system

In this study, mixed species biofilm formation including sulphate reducing bacteria (SRB) on the galvanized steel surfaces and also microbiologically influenced corrosion (MIC) of galvanized steel were observed in a model recirculating cooling water system during 10 months. A biofilm which had a heterogeneous structure formed on galvanized steel coupons. The results suggested that galvanized steel was corroded by microorganisms as well as SRB in the biofilm. Extracellular carbohydrate was degraded and quantities of carbohydrate were positively correlated with the weight loss. The concentrations of zinc in the biofilm showed significant correlations with weight loss, carbohydrate amount and SRB count.     

Characterizing the effect of carbon steel exposure in sulfide containing solutions to microbially induced corrosion

This article compares the electrochemical effects induced by inorganic sulfide and sulfate reducing bacteria on the corrosion of carbon steel – a subject of concern for pipelines. Biological microcosms, containing varying concentrations of bioorganic content, were studied to investigate changes to the morphology of biofilms and corrosion product deposits. Raman analysis indicated mackinawite (FeS_1−x) was the dominant iron sulfide phase grown both abiotically and biotically. A fascinating feature of biological media, void of an organic electron donor, was the formation of putative nanowires that may be grown to acquire energy from carbon steel by promoting the measured cathodic reaction.     

A novel Schiff base-based cationic gemini surfactants: Synthesis and effect on corrosion inhibition of carbon steel in hydrochloric acid solution

The corrosion inhibition characteristics of the synthesized cationic gemini surfactants, namely bis(p-(N,N,N-decyldimethylammonium bromide)benzylidene thiourea (10-S-10), bis(p-(N,N,N-dodecyldimethylammonium bromide)benzylidene thiourea (12-S-12) and bis(p-(N,N,N-tetradecyldimethylammonium bromide)benzylidene thiourea (14-S-14) on the carbon steel corrosion in 1 M hydrochloric acid have been investigated at 25 °C by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The inhibition efficiencies obtained from all methods employed are in good agreement with each other. The obtained results show that compound 14-S-14 is the best inhibitor with an efficiency of 97.75% at 5 × 10⁻³ M additive concentration. Generally, the inhibition efficiency increased with increase of the inhibitor concentration. Changes in impedance parameters (charge transfer resistance, R_ct, and double-layer capacitance, C_dl) were indicative of adsorption of 14-S-14 on the metal surface, leading to the formation of a protective film. The potentiodynamic polarization measurements indicated that the inhibitors are of mixed type. The adsorption of the inhibitors on the carbon steel surface in the acid solution was found to obey Langmuir’s adsorption isotherm. The free energy of adsorption processes were calculated and discussed. The surface parameters of each synthesized surfactant were calculated from its surface tension including the critical micelle concentration (CMC), maximum surface excess (Γ_max) and the minimum surface area (A_min). The free energies of micellization (ΔG^o_mic) were calculated. The surface morphology of carbon steel sample was investigated by scanning electron microscopy (SEM).     

Corrosion monitoring of mild steel in sulphuric acid solutions in presence of some thiazole derivatives – Molecular dynamics, chemical and electrochemical studies

The physical behavior of three selected thiazole derivatives, namely 2-Amino-4-(p-tolyl)thiazole (APT), 2-Methoxy-1,3-thiazole (MTT) and Thiazole-4-carboxaldehyde (TCA) at iron (1 1 0) surface dissolved in aqueous solution were studied via molecular dynamics (MD) simulations. From the calculated binding energies, APT showed preferred adsorption on the steel surface among the three tested thiazole derivatives. The inhibition performance of the three thiazoles on the corrosion of mild steel in 0.5 M H₂SO₄ solutions was investigated at 25 °C. Measurements were conducted under various experimental conditions using weight loss, Tafel polarization and electrochemical impedance spectroscopy. Electrochemical frequency modulation (EFM) technique was also employed here to make accurate determination of the corrosion rates and test validation of the Tafel extrapolation method for measuring corrosion rates. Polarization curves showed that the three thiazole derivatives were of mixed-type inhibitors for mild steel corrosion in 0.5 M H₂SO₄ solution. EFM results were in agreement with other traditional chemical and electrochemical techniques used in corrosion rate measurements. Chemical and electrochemical measurements are consistent with computational study that APT is the most effective inhibitor among the tested thiazoles.     

Corrosion behaviour of bulk ultra-fine grained AZ91D magnesium alloy fabricated by equal-channel angular pressing

Effect of microstructure change on corrosion behaviour of equal-channel angular pressed (ECAPed) AZ91D Mg alloy was investigated. The ECAPed alloy with ultra-fine grained (UFG) α-phase matrix and refined β-phase particles displays a significantly lower corrosion resistance, resulting in more pits after in-situ corrosion, higher mass-loss rate immersed in NaCl solution, larger I_corr values in polarization curves and lower fitted R_t values in EIS plots. Two factors weaken the corrosion resistance: the first is the strains-induced crystalline defects providing the α-phase matrix more corrosion activation, the second is the refined β-phase particles losing barrier to the corrosion propagation in α-phase matrix.     

Corrosion behaviour of AISI type 304L stainless steel in nitric acid media containing oxidizing species

The corrosion behaviour of AISI type 304L stainless steel (SS) in different concentration of 0.01 M, 1 M and 5 M HNO₃ in presence of oxidizing ions at different temperatures has been evaluated. The main objective of this study is to assess the corrosion resistance of type 304L SS in non-radioactive conditions encountered during storage of liquid nuclear waste. Electrochemical impedance spectroscopy (EIS) and laser Raman spectroscopy (LRS) has clearly brought out the deleterious effect of oxidizing species on the passive film leading to increased corrosion along with increase in HNO₃ concentration and higher temperature.     

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.     

Effect of temperature and fluid velocity on corrosion mechanism of low carbon steel in presence of 2-hydrazino-4,7-dimethylbenzothiazole in industrial water medium

The corrosion inhibition of 2-hydrazino-4,7-dimethylbenzothiazole on low carbon steel in industrial water has been investigated at different temperatures and fluid velocities at different concentrations of the inhibitor using mass loss, potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The results showed that corrosion resistance increased by increasing the inhibitor concentration. Optimization of the three variables has been made and correlating the results obtained using Box–Wilson statistical method. The adsorption process on low carbon steel surface obeys Flory–Huggins isotherm. The values of ΔG_ads obtained suggest that, the adsorption process of 2-HMBT on low carbon steel is chemisorption. The activation energy increased with increasing the concentration of inhibitors leading to decrease of the pre-exponential factor, and the entropy of activation increased negatively in the presence of inhibitor. SEM was used to identify the film formed on the metal surface.     

A peculiar cathodic process during iron and steel corrosion in sulfate reducing bacteria (SRB) media

Features related to the cathodic reduction of iron sulfides precipitation on iron surface during its exposure to SRB culture were studied. Electrochemical measurements were performed with pure iron and platinum electrodes plated with a thin iron film in de-aerated SRB culture. The study reveals that iron sulfide precipitation is being cathodically reduced just below a potential of −0.1 V_SCE, and if iron corrosion process occurs at potentials below that threshold potential, then the reduction of iron sulfide may provide an alternative cathodic depolarization mechanism in SRB. This cathodic process can maintain iron and corrosion at potentials above RHE potential.     

A comparative study on the corrosion behaviour of 304 austenitic stainless steel in sulfamic and sulfuric acid solutions

Potentiodynamic polarization and EIS have been employed to compare the corrosion behaviour of 304 stainless steel in NH₂SO₃H and H₂SO₄ solutions. Corrosion tests were carried out as a function of the acid’s concentration (0.1-0.5 M) and solution temperature (20-60 ^oC). The corrosion rate is higher in H₂SO₄ than in H₂NSO₃H in all concentrations and temperatures. Values of the activation energy (E_a) revealed that the corrosion process is faster in H₂SO₄ than in NH₂SO₃H solution. EIS data showed that the display of Nyquist plots, and hence the mechanism of corrosion, depends not only on the acid concentration but also on the solution temperature. In 0.1 M concentration, the equivalent circuits R_e(R_ctQ_dl) and R_e(R_ctQ_dl)(RQ)_ads describe the corrosion systems in H₂NSO₃H and H₂SO₄ solutions respectively. At concentrations ?0.2 M, the equivalent circuit R_e(R_ctQ_dl)Q_diff is applicable. Adsorption of the counter ion of the acid on the steel surface and the stability of the surface complex may explain the observed corrosion rates.     

Specification of sulfate reducing bacteria biofilms accumulation effects on corrosion initiation

The accumulation process of sulfate reducing bacteria (SRB) biofilms established in anaerobic stagnant batch bioreactors on the surface of carbon steel and the nutrient transport and corrosion products distribution in it were characterized by X‐ray Photoelectron Spectroscopy (XPS). In addition, the corrosion occurrence and development of carbon steel under SRB biofilm was investigated by Electrochemical Impedance Spectroscopy (EIS) in‐situ. The results show that the thickness of SRB biofilms increases exponentially with time in the beginning and after 14 days reaches a maximum. From then on, the accumulation rate decreases to zero. In mature biofilms, SRB dispersed throughout the biofilm. In the inner layer near the substrate, due to the high sulfate‐reducing activity of SRB, corrosion products such S^2?, H₂S and organic acid are present, which lead to corrosion occurrence and development. In the outer layer of the biofilm SRB can also reduce the SO^2?₄ to SO^2?₃ and S₂O^2?₃. This metabolism process enhances the Fe²⁺ transfer from the inner to the outer side. The activity of SRB in the biofilm plays a key role in the initial corrosion process.