Pit formation on stainless steel surfaces pre-treated with biosurfactants produced by Pseudomonas fluorescens

Today, it is widely established that the surface tension of water can be reduced by some microorganisms capable of synthesizing surface-active compounds called biosurfactants (BS). BS characteristics depend on the microorganism that produces them and therefore, on the microorganism culture conditions.Some studies on chemical surfactants have shown that the adsorption of surface-active compounds plays a major role in corrosion; indeed they are used as a good corrosion inhibition tool.The purpose of this study was first, to estimate the importance and behavior of the stainless steels passive film on the adsorption of BS, produced by the Gram negative bacteria Pseudomonas fluorescens, and secondly, to study the impact of these treatments on the pitting corrosion.In this paper, the galvanostatic polarization technique, used as accelerated method for determining the characteristic pit potentials on stainless steels, is examined. Pit growth, shape and cover formation were also observed. The surface topography of the corroded specimens was investigated using field emission scanning electron microscopy (FESEM).     

The electrochemical behaviour of stainless steel AISI 304 in alkaline solutions with different pH in the presence of chlorides

Nowadays, stainless steel reinforcements appear as an effective solution to increase the durability of reinforced concrete structures exposed to very aggressive environments. AISI 304 is widely used for this purpose. Although the improved durability of reinforcing AISI 304, when compared to carbon steel, there is a high probability of pitting susceptibility in the presence of chlorides. Thus, the present work aims at studying the passivation and passivation breakdown of AISI 304 in alkaline solutions of different pH (pH from 13 to 9), simulating the interstitial concrete electrolyte. These solutions were contaminated with different concentrations of chloride ions (3% and 10%, as NaCl). The electrochemical behaviour was evaluated by d.c. potentiodynamic polarization and by electrochemical impedance spectroscopy (EIS).The morphological features and the changes observed in the surface composition were evaluated by Scanning Electron Microscopy (SEM) together with EDS chemical analysis.The results evidence that pH plays an important role in the evolution of the film resistance and charge transfer processes. Moreover, the effect is highly dependent upon the chloride content and immersion time.     

Electrochemical reduction of oxygen catalyzed by Pseudomonas aeruginosa

Pseudomonas aeruginosa has already been shown to catalyze oxidation processes in the anode compartment of a microbial fuel cell. The present study focuses on the reverse capacity of the bacterium, i.e. reduction catalysis. Here we show that P. aeruginosa is able to catalyze the electrochemical reduction of oxygen. The use of cyclic voltammetry showed that, for a given range of potential values, the current generated in the presence of bacteria could reach up to four times the current obtained without bacteria. The adhesion of bacteria to the working electrode was necessary for the catalysis to be observed but was not sufficient. The electron transfer between the working electrode and the bacteria did not involve mediator metabolites like phenazines. The transfer was by direct contact. The catalysis required a certain contact duration between electrodes and live bacteria but after this delay, the metabolic activity of cells was no longer necessary. Membrane-bound proteins, like catalase, may be involved. Various strains of P. aeruginosa, including clinical isolates, were tested and all of them, even catalase-defective mutants, presented the same catalytic property. P. aeruginosa offers a new model for the analysis of reduction catalysis and the protocol designed here may provide a basis for developing an interesting tool in the field of bacterial adhesion.     

Electrochemical behaviour of an AISI 304L stainless steel implanted with nitrogen

In this paper the electrochemical behaviour of AISI 304L stainless steel implanted with nitrogen is studied in alkaline media and chloride-containing media, and it is compared with the behaviour of the unimplanted material. Implantation was done at a saturation dose (4 × 10¹⁷ ions cm⁻²) at an acceleration voltage of 150 keV. The results show a clear improvement of the corrosion resistance for the implanted specimens. No pitting potential is observed in the alkaline media or in the neutral media containing high chloride concentration. The improved corrosion resistance is presumed to be due to the modifications that N⁺ implantation induces in the passive layer that is naturally formed on the alloy. XPS analysis reveals Ni⁰ and Cr³⁺ enrichment in this passive layer. Moreover, a carbon-rich layer is found at the outermost part of the passive layer. The presence of this outermost layer is verified with electrochemical impedance measurements and SEM observations.     

Surface and electrochemical characterization of pitting corrosion behaviour of 304 stainless steel in ground water media

The effectiveness of aminotrimethylidene phosphonic acid (ATMP) as a corrosion inhibitor in association with a bivalent cation like Zn²⁺ and non-ionic surfactant like polyoxyethylene sorbitan monooleate (Tween 80) were investigated by measuring corrosion losses using electrochemical techniques. The corrosion of 304 stainless steel in the ground water medium was inhibited by complexation of the inhibitor. A combined inhibition effect was achieved by adding both ATMP and Zn²⁺ along with Tween 80. The formulation functioned as a mixed type inhibitor. The synergistic effect of the inhibitor compound is calculated. Luminescence spectra, FTIR spectra, XRD, XPS and scanning electron microscopic studies were carried out to understand the mode of corrosion inhibition and also the morphological changes on the metal surface.     

Impedance investigation of passive 304 stainless steel in the pit pre-initiation state

The results of impedance measurements on stainless steel 304L by classical and dynamic electrochemical impedance spectroscopy (DEIS) have been presented. The investigation was focused on a transition of steel from passive state to the initial stage of pit formation. Based on the evolution of electrical parameters of the equivalent circuit it has been stated that the most probable mechanism of pit creation is the film-breaking model.     

Microbial electrocatalysis with Geobacter sulfurreducens biofilm on stainless steel cathodes

Stainless steel and graphite electrodes were individually addressed and polarized at −0.60 V vs. Ag/AgCl in reactors filled with a growth medium that contained 25 mM fumarate as the electron acceptor and no electron donor, in order to force the microbial cells to use the electrode as electron source. When the reactor was inoculated with Geobacter sulfurreducens, the current increased and stabilized at average values around 0.75 A m⁻² for graphite and 20.5 A m⁻² for stainless steel. Cyclic voltammetry performed at the end of the experiment indicated that the reduction started at around −0.30 V vs. Ag/AgCl on stainless steel. Removing the biofilm formed on the electrode surface made the current totally disappear, confirming that the G.sulfurreducens biofilm was fully responsible for the electrocatalysis of fumarate reduction. Similar current densities were recorded when the electrodes were polarized after being kept in open circuit for several days. The reasons for the bacteria presence and survival on non-connected stainless steel coupons were discussed. Chronoamperometry experiments performed at different potential values suggested that the biofilm-driven catalysis was controlled by electrochemical kinetics. The high current density obtained, quite close to the redox potential of the fumarate/succinate couple, presents stainless steel as a remarkable material to support biocathodes.     

Electrochemical activity of Geobacter sulfurreducens biofilms on stainless steel anodes

Stainless steel was studied as anode for the biocatalysis of acetate oxidation by biofilms of Geobacter sulfurreducens. Electrodes were individually polarized at different potential in the range −0.20 V to +0.20 V vs. Ag/AgCl either in the same reactor or in different reactors containing acetate as electron donor and no electron acceptor except the working electrode. At +0.20 V vs. Ag/AgCl, the current increased after a 2-day lag period up to maximum current densities around 0.7 A m⁻² and 2.4 A m⁻² with 5 mM and 10 mM acetate, respectively. No current was obtained during chronoamperometry (CA) at potential values lower than 0.00 V vs. Ag/AgCl, while the cyclic voltammetries (CV) that were performed periodically always detected a fast electron transfer, with the oxidation starting around −0.25 V vs. Ag/AgCl. Epifluorescent microscopy showed that the current recorded by chronoamperometry was linked to the biofilm growth on the electrode surface, while CVs were more likely linked to the cells initially adsorbed from the inoculum. A model was proposed to explain the electrochemical behaviour of the biofilm, which appeared to be controlled by the pioneering adherent cells playing the role of “electrochemical gate” between the biofilm and the electrode surface.     

MIC of stainless steel in freshwater and the cathodic behaviour of biomineralized Mn-oxides

Microbially influenced corrosion by manganese oxidizing microorganisms (MIC by MOMOs) is a corrosion phenomenon occurring in freshwater systems affecting stainless steels. Typically, chloride induced corrosion is observed at chloride concentrations normally not considered as critical. The initiation of corrosion is attributed to an anodic shift of the open circuit potential of the passive stainless steel caused by manganese dioxide biomineralized by the specific organisms. However, not only the potential of the passive steel seems of interest. For the stabilization of localized corrosion, the ability of the cathodic reaction to drive enough current for promoting the switch from metastable pitting to stable pit growth is considered important. Consequently, experiments have been carried out in order to compare the dynamic cathodic properties of the usual oxygen reduction reaction with that of biofilm incorporating biomineralized MnO₂. The results indicate a significantly better cathodic performance of such biofilm which might explain the fast and extensive damages observed in certain cases of MIC by MOMOs.     

Poly(N-ethylaniline) coatings on 304 stainless steel for corrosion protection in aqueous HCl and NaCl solutions

Poly(N-ethylaniline) (PNEA) coatings were grown by potentiodynamic synthesis technique on 304 stainless steel (SS) alloy from 0.1 M of N-ethylaniline (NEA) in 0.3 M oxalic acid solution. Characterization of adhesive and electroactive PNEA coatings was carried out by cyclic voltammetry, FT-IR spectroscopy and scanning electron microscopy (SEM) techniques. The protective properties of PNEA coatings on SS were elucidated using linear anodic potentiodynamic polarization, Tafel and electrochemical impedance spectroscopy (EIS) test techniques, in highly aggressive 0.5 M HCl and 0.5 M NaCl solutions. Linear anodic potentiodynamic polarization test results proved that PNEA coating improved the degree of protection against pitting corrosion in HCl and NaCl solutions. Tafel test results showed that PNEA coating appears to enhancement protection for SS in 0.5 M NaCl and 0.5 M HCl solutions. However, according to long-term EIS results, PNEA coating is better for the protection of SS electrodes during the long immersion period in NaCl compared to that in HCl medium.     

Influence of nanocrystallization on pitting corrosion behavior of an austenitic stainless steel by stochastic approach and in situ AFM analysis

The pitting corrosion behavior of an austenitic stainless steel nanocrystalline (NC) coating, fabricated by magnetron sputtering as well as that of the conventional polycrystalline (PC) alloy have been investigated in 3.5% NaCl solution by stochastic approach and in situ atomic force microscopy (AFM). The results indicate that the pitting corrosion resistance of the NC coating was much higher than that of the PC alloy with higher prevalence of metastable pits and lower rates of stable pit nucleation and growth. The influence of nanocrystallization on the pit initiation and pit growth processes has been discussed according to the in situ AFM observations.     

DEIS assessment of AISI 304 stainless steel dissolution process in conditions of intergranular corrosion

Results presented in this paper are first that demonstrate instantaneous impedance changes versus reactivation potential detected by means of dynamic electrochemical impedance spectroscopy (DEIS) technique for AISI 304 stainless steel dissolution process proceeding during intergranular corrosion (IG) in 0.5 M SO₄²⁻ + 0.01 M KSCN solution of different pHs. Application of DEIS method made it possible to evaluate dynamic changes of the examined system's impedance in conditions of IG. As a result, controlling stage of the overall rate of AISI 304 SS dissolution process was determined. Moreover, the paper proposes an alternative way of assessment of AISI 304 SS dissolution rate during intergranular corrosion based on approximation to theory of iron dissolution in sulfuric acid medium. Simultaneously, on the basis of the DEIS measurements it was possible to obtain information about the degree of sensitization (DOS) of the examined material. Accordingly, performed researches revealed the advantage of the DEIS technique over the electrochemical potentiokinetic reactivation (EPR) tests when investigating intergranular corrosion process.     

Pitting mechanism on an austenite stainless steel nanocrystalline coating investigated by electrochemical noise and in-situ AFM analysis

The pitting corrosion behavior of an austenite stainless steel with polycrystalline (PC) and nanocrystalline (NC) microstructure in 3.5% NaCl solution was investigated by electrochemical noise (EN) and in-situ atomic force microscopy (AFM) under anodic potential. The power spectral density (PSD) and wavelet transform have been employed to analyze the EN data. The pitting corrosion resistance of the NC coating was much higher than that of the PC alloy, with different pitting mechanisms observed for both specimens; a slow metastable pit generation and healing for the PC alloy and a fast metastable pit initiation and death for the NC coating. There was good conformity between the EN and the in-situ AFM analysis. The pitting corrosion mechanism has been discussed according to the EN analysis and the in-situ AFM observations.     

Corrosion behavior of titania films coated by liquid‐phase deposition on AISI304 stainless steel substrates

Fouling deposition and localized corrosion on the heat‐transfer surfaces of the stainless steel equipments often simultaneously exist, which can introduce additional thermal resistance to heat‐transfer and damage heat‐transfer surfaces. It is a good anticorrosion way to coat a barrier layer of certain materials on the metal surface. In this article, the TiO₂ coatings with nanoscale thicknesses were obtained by liquid‐phase deposition method on the substrates of AISI304 stainless steel (ASS). The coating thickness, surface roughness, surface morphology, crystal phase, and chemical element were characterized with the film thickness measuring instrument, roughmeter, atomic force microscopy, field emission scanning electron microscopy, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy analyzer, respectively. Corrosion behavior of the TiO₂ coatings was evaluated by potentiodynamic polarization, cyclic voltammograms scanning, and electrochemical impedance spectroscopy tests with the mixed corrosion solution composed of 3.5 wt. % NaCl and 0.05 M NaOH. It is shown that the TiO₂ coating is composed of the nanoparticles with smooth, crack‐free, dense, and uniform surface topography; the roughness of coating surface increases slightly compared with that of the polished ASS substrate. The anatase‐phase TiO₂ coatings are obtained when sintering temperature being varied from 573.15 to 923.15 K and exhibit better anticorrosion behavior compared with ASS surfaces. The corrosion current density decreases and the polarization resistance increases with the increase of the coating thickness. The corrosion resistance of the TiO₂ coatings deteriorates with the increase of the corrosion time. The capacitance and the resistance of the corrosion product layer between the interface of the ASS substrate and the TiO₂ coating are found after the corrosion time of 240 h. A corrosion model was introduced, and a possible new explanation on the anticorrosion mechanisms of the TiO₂ coating was also analyzed. The corrosion mechanism of the TiO₂ coating might comply with the multistage corrosion process. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1907–1920, 2012     

The influence of bacteria on the passive film stability of 304 stainless steel

The stability of stainless steel 304 in the presence of aerobic and anaerobic bacteria was investigated in a continuous flow system using electrochemical impedance spectroscopy and scanning electron microscopy (SEM) examinations. The results show that the open circuit potential (OCP) of stainless steel was ennobled (shifted in the electropositive direction) by about +150 mV in the presence of the aerobic bacteria. The observed change of OCP in the electropositive direction can be explained by an increase in the rate of the cathodic reaction. Also the presence of an aerobic biofilm led to a decrease in the polarization resistance of stainless steel is not only due to the growth of micropits, as shown from SEM micrographs, but also due to thinning of the passive film. In the presence of only Pseudomonas fragi, the electrochemical impedance response showed a capacitive behavior with RP on the order of 500 kΩ. The addition of anaerobic sulfate reducing bacteria (SRB) to the test medium decreased RP to 12 kΩ due to an increase in localized corrosion, as indicated by SEM examination.     

Joining of Cf/SiC composite and 304 stainless steel assisted by surface honeycomb modification

A novel surface honeycomb modification was developed by pre-oxidizing the C_f/SiC composite, and the honeycomb modified C_f/SiC composite and stainless steel were brazed with AgCuTi filler. Results showed that a honeycomb-like surface with dense pores could be obtained when the C_f/SiC composite was air-oxidized at 700°C. During the brazing process, the liquid filler infiltrated into the pores and formed an infiltrated area, which not only significantly increased the bonding area between the reaction layer and the C_f/SiC composite, but also effectively hindered the crack propagation due to the nailing/pinning effect. The Finite Element simulation displayed that the infiltrated area transferred the stress concentration away from the reaction layer, dispersed the residual stress and reduced the corresponding stress value. As the result, the maximum shear strength of the joint reached 158MPa, which is multiple times higher than the joint without surface honeycomb modification.     

AISI 304 L stainless steel decontamination by a corrosion process using cerium IV regenerated by ozone Part I: Study of the accelerated corrosion process

This paper describes the study of a new decontamination process of AISI 304L stainless steel from dismantled nuclear power plants. A very thin active contaminated surface layer was stripped from the underlying metal by corrosion in a solution of nitric acid with the addition of cerium nitrate. The Ce⁴⁺/Ce³⁺ concentration ratio was initially equal to unity and ozone/oxygen bubbles were used to regenerate Ce³⁺ ions into Ce⁴⁺ ions. The study was performed in a laboratory cell prior to preliminary optimization in a three-litre reactor. The objective was to obtain a corrosion rate of about 10 micrometers per day. This target was reached in 10^–2 mol l^–1 of cerium nitrate with bubbling of a 1.56 g h^–1 ozone flow in a 60 l h^–1 total gas flow. The corrosion rate depended essentially on the Ce⁴⁺ concentration. The stainless steel exhibited intergranular corrosion. The corrosion rate was monitored by measuring the solution oxidizing potential using a precious metal electrode.     

Critical pitting and repassivation temperatures for duplex stainless steel in chloride solutions

Both the critical pitting temperature (CPT) and critical repassivation temperature (T_r) for two kinds of duplex stainless steels (DSS, namely UNS S31803 and UNS S32750) were investigated in 1 mol/L NaCl solution using the cyclic thermammetry method. Potentiodynamic anodic polarization technique was employed to validate the cyclic thermammetry technique. In addition, the site of pitting nucleated preferentially on the DSS had been confirmed by scanning electron microscopy (SEM). The results demonstrated that there exhibits a hysteresis loop in cyclic thermammetry curve, revealing that the propagating pits could repassivate during the cooling half-cycle. The CPT and T_r for UNS S31803 were 59.6 °C and 36.5 °C, whilst the CPT and T_r for UNS S32750 were 87.5 °C and 70.5 °C, respectively. Pitting was always observed preferentially in the austenite phase. The results can be partially explained based on the changes in chemical composition of ferrite and austenite phases. Moreover, a semi-quantitative model is proposed to explain the existence of T_r.     

Protection of type 430 stainless steel against pitting corrosion by ladder conductive polymer

Poly(o-phenylenediamine) (PoPD) was electropolymerized by cyclic voltammetry (CV) on 430 stainless steel from sulfuric acid solution containing o-phenylenediamine monomer. The formation of the polymer film is slower than that of polyaniline (PANI) film. Transparent and compact layers (∼1.0 μm) of PoPD deposited after 100 cycles, while thicker (∼3 μm), grainy and porous layers of PANI formed after 50 cycles. The PoPD layers protect the steel substrate from pitting in 3% NaCl but the layers of PANI fail, and pitting and crevice corrosion were observed on the steel surface. Both polymers keep the steel substrate in a passive state in sulfuric acid. After aging in acid solution the underlying oxides were investigated after peeling off the polymer layers; this showed an excellent passive film formed under PoPD. The passive steel was completely free from pitting after immersion in the chloride solution for 1 week.     

304不锈钢管焊缝区碱性腐蚀的电化学噪声检测

利用电化学电位噪声检测304不锈钢管焊缝区在50%NaOH碱液沸腾温度下腐蚀过程的电位噪声谱,观测相应的腐蚀形貌,分析电化学噪声谱特征参数。结果表明：实验过程中焊缝处腐蚀电位呈下降趋势;发生局部腐蚀裂纹时,电位噪声时域谱振幅较大,出现暂态峰;经快速傅里叶变换（FFT）后的功率密度（PSD）谱出现高频白噪声水平,PSD谱高频线性部分的斜率K>-20 dB·dec^-1。测试室温碱液中304不锈钢管焊缝处的电化学噪声表明,不同腐蚀状态的焊缝试样腐蚀电位及噪声时域谱特征不同,可利用K值定性判定是否发生局部腐蚀,为现场检测奠定基础。