In situ AFM detection of pit onset location on a 304L stainless steel

A set-up combining an AFM and an electrochemical cell has been used to study in situ the local corrosion of a 304L stainless steel in an aqueous chloride-containing solution. The focus was made on the sites where pits were initiated under controlled potential in order to establish whether or not the pits were randomly distributed at the nanoscale. Grain boundaries and surface stoichiometric inhomogeneities appeared to concentrate pit onsets significantly. The influence of the mechanical history of the material, especially soft surface strain hardening, on the location of the first pits has been shown. The study revealed that 70% of the pits initiated at strain hardened areas resulting from mechanical polishing. A plausible model has been suggested to explain such a behaviour.     

Corrosion behavior of TiC particle-reinforced 304 stainless steel

TiC particle-reinforced 304 stainless steels were prepared using a new developed in situ technology and their corrosion behavior was compared with that of 304SS in 5 wt.% HCl solution. As compared to 304SS, E_corr, E_pit and E_rp values had shifted to a more negative region in 304SS containing TiC, indicating faster corrosion rate by TiC addition. The addition of TiC particles to 304SS resulted in no rapid pit propagation but maintained a high corrosion rate in the whole immersion time investigated.     

Surface chemistry and corrosion behaviour of 304 stainless steel in simulated seawater containing inorganic sulphide and sulphate-reducing bacteria

Although many studies have been carried out regarding the role of sulphide anions in promoting microbial corrosion of various metal substrates, very little is known about the differences between inorganic sulphide and biogenically-derived sulphide by sulphate-reducing bacteria (SRB) and what the reasons for differing corrosion behaviour between the two types of sulphide may be towards common metals. In this study, various electrochemical and surface analytical techniques were employed to study the effect of the inorganic and biogenic sulphide (active SRB present) on the surface chemistry and corrosion behaviour of 304 stainless steels in a simulated seawater-based modified Baar’s (SSMB) medium. Clear differences in the surface chemistry of the sulphurised passive film by inorganic and biogenic sulphide (active SRB present) were quantified by X-ray photoelectron spectroscopy (XPS). The transformation of metal sulphides in abiotic and biotic sulphide solutions with the exposure time was correlated with different corrosion behaviour of 304 stainless steels.     

An experimental study of crevice corrosion behaviour of 316L stainless steel in artificial seawater

The effects of applied torque on corrosion behaviour of 316L stainless steel with crevices were investigated using the cyclic potentiodynamic polarization method. Three kinds of crevices (316L-to-polytetrafluoroethylene, 316L-to-fluoroelastomeric and 316L-to-316L) were tested in artificial seawater at 50 °C. Corroded surface morphology was also investigated using scanning electron microscopy. Results indicate similar trends in crevice corrosion susceptibility with increasing applied torque. Among the three crevices, the 316L stainless steel specimen, coupled to the 316L stainless steel crevice former, is the most susceptible to crevice corrosion.     

Eradication of the corrosion-causing bacterial strains Desulfovibrio vulgaris and Desulfovibrio desulfuricans in planktonic and biofilm form using photodisinfection

Oil and gas pipelines often fail prematurely due to “microbiologically-influenced corrosion” (MIC). This occurs when free-floating bacteria collect on the inner pipeline surface, eventually forming complex adherent biofilms. Photodisinfection is an effective antimicrobial approach for several biomedical applications. This study evaluated the antibacterial efficacy of photodisinfection against two sulfate-reducing bacterial strains implicated in the process of MIC. Results showed that treatment reduced planktonic bacterial viability by >99.99%. Treatment of biofilms reduced viability by 99.9%, which was greater than the antibacterial effect observed using the biocide benzalkonium chloride under similar exposure parameters. These results suggest that photodisinfection may be useful in addressing MIC in industrial pipelines.     

Acoustic emission during pitting corrosion of 304 stainless steel

Acoustic emission (AE) during pitting corrosion of 304 stainless steel (304 SS) in H₂SO₄ solutions with different pH values and Cl⁻ concentrations was studied. Two types of AE signals are detected in all solutions. Each type of signals is characterized by AE parameters (rise time, counts number, duration and amplitude) and waveform carefully. It is believed that the hydrogen bubbles evolution inside the pits is the AE source.     

The effect of annealing on the corrosion behaviour of 444 stainless steel for drinking water applications

In this study, the corrosion behaviour of annealed and not annealed AISI 444 ferritic stainless steel in tap water with and without addition of selected concentrations of chloride ions was investigated. Cyclic potentiodynamic macro (large area) and micro (small area) polarization measurements (CPP), salt spray test, SEM and EDS analysis were employed to evaluate the pitting and crevice corrosion susceptibility of annealed and not annealed AISI 444. The results obtained indicate that annealing does not improve the resistance to pitting and crevice corrosion. Moreover, micro CPP indicates local susceptibility to pitting on both annealed and not annealed materials; such susceptibility was not evident from macropolarization tests.     

Combined effect of resistance spot welding and post-welding sensitization on the degree of sensitization of AISI 304 stainless steel

This work studies the combined effect of resistance spot welding (RSW) and post-welding sensitization on the degree of sensitization (DOS) of AISI 304 stainless steel (SS) by using EPR and DLEPR tests. The combined effect of RSW and post-welding sensitization at 750 °C gives rise to an overall DOS that: (i) is lower than that of the state without prior welding; (ii) that decreases initially with increasing sensitization time but then increases. This behaviour is due to the fact that the interdendritic corrosion (IDC) located in the weld metal decreases with increasing sensitization time.     

Effect of biofilm on ennoblement and localized corrosion of stainless steel in fresh dam-water

AISI 304 stainless steel specimens were exposed in-situ to fresh dam-water for nearly 2 years. Open circuit potential (OCP) of the specimens becomes remarkably ennobled after exposure for about 40 days. The ennobled OCP of coupons is greatly affected by both immersion depth and sunlight. It is found that ammonium, nitrate, nitrite and chloride ions are enriched in the biofilm. It is suggested that the reduction of nitrate may be partly responsible for the OCP ennoblement. Localized corrosions at welds and crevices of specimens are attributed to both the OCP ennoblement of specimens and the chloride ion enrichment in the biofilm.     

Influence of ultrasound on pitting corrosion and crevice corrosion of SUS304 stainless steel in chloride sodium aqueous solution

The change of polarization curves and surface morphologies of SUS304 stainless steel was investigated in 3.5 mass% NaCl solution with or without the application of ultrasound (US). As the result, both the pitting corrosion and the crevice corrosion were largely suppressed by the application of US. The reason is attributed to the decrease in the concentration of hydrogen and chloride ions in pits or in the crevice by removing the corrosion product and stirring the liquid there.     

Oxidation of stainless steel 304L in carbon dioxide

Oxidation of 304L stainless steel in a carbon dioxide atmosphere at 10⁵ Pa has been studied. Between 1193 and 1293 K the oxidation kinetics exhibit first a rapid increase, then a parabolic behaviour with apparent activation energy of (209 ± 8) kJ mol⁻¹ and obeys a Langmuir pressure law. After 1.15 mg cm⁻², the kinetics become almost linear.The reaction products are chromia at the grain boundaries, wüstite (Fe_1−xO) on the surface for weight gains greater than 0.30 mg cm⁻² and chromite. The very complex reaction mechanism takes into account random buckling for weight gains >1.15 mg cm⁻².     

Improving the intergranular corrosion resistance of 304 stainless steel by grain boundary network control

The grain boundary network (GBN) was controlled by grain boundary engineering (GBE) in a 304 stainless steel. The total length proportion of Σ3ⁿ coincidence site lattice (CSL) boundaries was increased to more than 70% associating with the formation of large size highly twinned grain-cluster microstructure. Only coherent twin boundaries (Σ3_c) were found to be resistant to intergranular corrosion (IGC) and only such boundaries could be termed “special” ones. The improvement of resistance to IGC of the GBE specimen can be attributed to the large size grain-clusters associated with high proportion of the Σ3ⁿ boundaries and the interconnected Σ3ⁿ-type triple junctions.     

Use of EPR test to study the degree of sensitization in resistance spot welding joints of AISI 304 austenitic stainless steel

The degree of sensitization (DOS) in resistance spot welding (RSW) joints is considered as the combined effect of intergranular corrosion (IGC) and transgranular corrosion (TGC) in the heat affected zone (HAZ) and of interdendritic corrosion (IDC) in the weld nugget (WN). The DOS is evaluated from electrochemical potentiokinetic reactivation (EPR) tests. The application of EPR test to RSW joints is optimized and an electrochemical minicell is used to study the effect of heat input on IDC in the WN.     

Influence of input power to vibrator and vibrator-to-specimen distance of ultrasound on pitting corrosion of SUS304 stainless steel in 3.5% chloride sodium aqueous solution

The pitting corrosion of SUSU304 steel can be suppressed by the application of a 19.5 kHz ultrasound (US) in 3.5% NaCl aqueous solution. At a constant vibrator-to-specimen distance of d = 76 mm equal to the wavelength, the suppression effect increased with the input power to vibrator and the largest effect was obtained at the power of I = 8. At constant input powers of I = 2 or 8, the suppression effect decreased with the increase in the vibrator-to-specimen distance, but the largest effect was obtained at d = 68 mm in each case of I = 2 and 8.     

In situ investigation of crevice corrosion on UNS S32101 duplex stainless steel in sodium chloride solution

The crevice corrosion of UNS S32101 in neutral 0.1 M NaCl solutions at room temperature was investigated directly by a facile method. Experimental results showed that both delayed and immediate crevice corrosion can be initiated. Morphology study indicated that the heaviest corrosion attack happened just below the passive/active boundary on the crevice wall. The relocation of the active dissolution regions during crevice corrosion was observed and explained by established theory. The mechanisms of the delayed and immediate types of crevice corrosion on UNS S32101 duplex stainless steel were discussed.     

Effect of annealing temperature on the corrosion behavior of duplex stainless steel studied by in situ techniques

The effects of the annealing temperature on the microstructure and the corrosion behavior of duplex stainless steel 2507 were investigated by means of magnetic force microscopy (MFM), scanning Kelvin probe force microscopy (SKPFM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The SEM results indicated that the volume fraction of the austenite phase decreased with the increased annealing temperature. SKPFM/MFM measurements conducted in air at the room temperature and an ambient relative humidity of about 25% showed a higher Volta potential of the paramagnetic austenite than that of the ferromagnetic ferrite. The in situ AFM observation in a hydrochloric acid solution provided solid evidence that corrosion preferentially occurred in the ferrite phase. The sample annealed at 1100 °C exhibited a greater Volta potential difference between the ferrite and austenite and a higher corrosion rate in the ferrite, while that annealed at 1150 °C had a smaller Volta potential difference and a lower corrosion rate. The relative nobility and microstructure change of two phases, as well as their corrosion behavior, can be explained by the effect of the composition of alloying elements.     

Microstructure and pitting corrosion resistance of annealed duplex stainless steel

The transition from metastable to stable pitting was studied in 0.5 M NaCl water solution for two cast duplex stainless steels under different microstructural conditions achieved by annealing in the range from 900 °C to 1200 °C. The ensuing microstructural changes in heat treated steels were defined and correlated with established pitting potentials (E_p) and sites of corrosion damage initiation. The variations in E_p have been discussed in terms of secondary phases precipitation. The critical condition for pit stability was quantified and used to select an appropriate microstructural state, resulting in the higher potential at which stable pit growth is first observed.     

Fatigue strength of 316L-type stainless steel in simulated body fluids

The fatigue strength of commercial SUS316L stainless steel was studied in PBS(−) (phosphate buffer solution) with different dissolved oxygen contents and CPBS (a 0.9 mass% NaCl-containing citric phosphate buffer solution) with different pH levels, i.e., 5.0, 6.0, and 7.5. The results obtained are as follows. (1) The fatigue behaviour in PBS(−) was hardly affected by the dissolved oxygen content. (2) The fatigue strength in a high-cycle region was much lower in CPBS of pH 7.5 than in PBS(−) of pH 7.5. (3) The fatigue strength in CPBS decreased with decreasing pH from 7.5 to 5.0.     

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.     

Acoustic emission during the electrochemical corrosion of 304 stainless steel in H2SO4 solutions

Acoustic emission (AE) behaviour during the electrochemical corrosion of 304 stainless steel (304SS) in H₂SO₄ solutions was studied. AE signals which related to transpassive dissolution are detected in solutions with low pH, and are very slightly influenced by current density and pre-strain. During hydrogen bubble evolution, a weak correlation exists between the AE signal amplitude and the hydrogen bubble diameter. The concept of potential – pH – AE diagram is proposed and such a diagram is drawn based on AE activity and b-values. The main mechanisms of AE sources which are transpassive dissolution and hydrogen bubble evolution, are also discussed.