Imitating seasonal temperature fluctuations for the H2S corrosion of 304L and 316L austenitic stainless steels

Temperature fluctuations are inevitable in sour oil and gas production. In this study, the H₂S corrosion of 304L and 316L alloys was investigated at pH 3 and temperatures of 20–60 °C using DC and AC electrochemical techniques. Two-fold increases in the corrosion rates of both alloys were reported with increases in temperature to 60 °C. In the 304L alloy, the surface layer was observed to be 3% rougher and 34% thicker than that of the 316L alloy. The two alloys exhibited different corrosion behaviors in the temperature ranges of 20–40 °C and 40–60 °C. Although the 316L alloy revealed a greater corrosion resistance at the free potential condition, the passivation on the 304L alloy was significantly greater than that of the 316L alloy at 40 °C and 15 ppm H₂S. The FeS₂ and combined FeS₂-MoS₂ compounds contributed to the surface layer constituents in the 304L and 316L alloys, respectively. The increase in temperature kinetically provided more favorable conditions for FeS₂ than MoS₂ formation, i.e. it had a relatively constructive effect on the 304L alloy passivation.     

An innovative specimen configuration for the study of Mg corrosion

Based on an analysis of galvanic corrosion research, the research reported herein was formulated to examine the measurement of polarisation curves for Mg to develop a methodology whereby reliable polarisation curves can be measured for Mg. Cathodic polarisation curves were measured for high purity Mg in 3.5% NaCl saturated with Mg(OH)₂ using three specimen types: (i) mounted specimens, (ii) specimens hung by fishing line and (iii) plug-in specimens. Cathodic polarisation curves were evaluated to yield the corrosion current density i_corr and the corresponding corrosion rate P_i, which was compared with the corrosion rate evaluated from hydrogen evolution measurements, P_H, and the corrosion rate evaluated by weight loss measurements, P_W. Mounted specimens produced values of corrosion rate, P_i, three times larger than values of corrosion rate, P_i, for plug-in specimens, attributed to crevice corrosion in the mounted specimens. Crevice corrosion in Mg is totally unexpected from prior research. The plug-in specimen configuration was designed to have no crevice and to allow simultaneous measurement of P_H and P_i; P_i was consistently less than P_H and indicated an apparent valence for Mg of 1.45 in support of the Mg corrosion mechanism involving the uni-positive Mg⁺ ion. The plug-in specimen has advantages for the study of Mg corrosion.     

H2S溶液中316L不锈钢TIG焊接头的腐蚀性能

文中通过极化曲线、交流阻抗、Mott-Schottky曲线、浸泡腐蚀试验等方法对316L奥氏体不锈钢TIG焊接头各区域在不同浓度H₂S溶液中的耐蚀性能进行了研究.极化曲线及交流阻抗结果表明,随着溶液中H₂S浓度的升高,焊接接头各区域的耐蚀性明显降低.另一方面对于相同浓度的H₂S溶液,316L基体的耐蚀性最好,其次是热影响区,焊缝区的耐蚀性最差.Mott-Schottky曲线结果表明,焊接接头在H₂S溶液中的表面钝化膜形成p-n结结构,掺杂浓度高达1022 cm-3,且掺杂浓度随H₂S浓度升高而增大,致使钝化膜防护性能降低.     

Corrosion and passivation of low-temperature nitrided AISI 304L and 316L stainless steels in acidified sodium sulphate solution

304L and 316L steels were nitrided at 425 °C for 30 h and examined at various depths in 0.1 M Na₂SO₄ acidified to pH 3.0. In the near-surface region with about 7-14 wt% N, at potentials of active state anodic currents were much higher than those for untreated steels, whereas in deeper regions with <7 wt% N the currents were only slightly increased in comparison with untreated steels or they were even lower in passive and transpassive states. Surface films were composed of oxygen-containing species on top and of Cr-N species in deeper layers. It is suggested that strong corrosion of near-surface regions is associated with nitride precipitates. Beneficial effect of low nitrogen concentrations can be due to initially accelerated corrosion which leads to larger amounts of passivating species and to the accumulation of corrosion resistant chromium nitrides.     

Corrosion behaviour of micro-plasma arc welded stainless steels in H3PO4 under flowing conditions at different temperatures

This paper studies the general corrosion behaviour of the micro-plasma arc welded AISI 316L stainless steel in phosphoric acid at different temperatures (25–60 °C) and at a Reynolds number of 1456. Galvanic corrosion has been studied using zero-resistance ammeter (ZRA) measurements and polarization curves (by the mixed potential theory). Results show that the microstructure of the stainless steel is modified due to the micro-plasma arc welding procedure. Coupled current density values obtained from polarization curves increase with temperature. ZRA tests present the highest i_G values at 60 °C; however, the values are very close to zero for all the temperatures studied. This is in agreement with the low value of the compatibility limit and of the parameter which evaluates the importance of the galvanic phenomenon. Both techniques present the most positive potentials at the highest temperature. This study reveals that micro-plasma arc welded AISI 316L stainless steels are appropriated working in the studied H₃PO₄ media from a corrosion point of view for all the temperatures analysed.     

Effects of dithionite ion on corrosion of type 304 stainless steel in sulphuric acid solution

Corrosion behaviour of type 304 stainless steel was investigated, with particular attention to additive effects of hydrosulphite (Na₂S₂O₄) on corrosion in 0.1 mol/l H₂SO₄ solution with various amounts of Na₂S₂O₄ up to 60 mmol/l.Corrosion of SUS304 occurred below pH 3.0 at 30 °C in a 0.1 mol/l H₂SO₄ solution in which Na₂S₂O₄ was added to 0.1-20 mmol/l. The maximum corrosion rate at 30 °C was measured as 7.2 g/m² h (7.9 mm/y) in 0.1 mol/l H₂SO₄-10 mmol/l Na₂S₂O₄ at pH 1.2. Microscopic surface observation revealed that active dissolution was accompanied by intergranular corrosion at the metal surface.The SUS304 was easily passivated in 0.1 mol/l H₂SO₄ solution with more than 30 mmol/l Na₂S₂O₄. NiS was detected in the passivated film.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.     

The chloride corrosion of austenitic stainless steels and of an inconel alloy in hot acidic media

Open circuit corrosion testing of austenitic stainless steels, AISI types 304, 310 and 316, and of an Inconel alloy in boiling 5% NaCl solution at pH 2.5 was carried out. The influences of aeration and the introduction of Cl₂ and/or H₂S were also examined. Cl₂ accelerated corrosion, pitting and crack formation whereas H₂S had an inhibiting effect on the corrosion rates and pitting but induced hydrogen attack, which appeared in the form of blisters on the surface specimen. H₂S in the absence of oxygen resulted in the growth of corrosion product on the specimen surface, instead of dissolution, but the cracking tendency also increased due to hydrogen penetration. Addition of trisodium phosphate to the corrosive solution markedly reduced pitting and lowered the corrosion rate by approximately half. Throughout the various tests it was found that the resistance of different alloys to hot chloride corrosion was in the order 310 > 316 > 304 > Inconel.     

Corrosion of biomaterials: anodic treatment and evaluation of 316L stainless steel in simulated body fluid

The influence of electropolishing at different conditions on the electrochemical behaviour of 316L stainless steel (316L SS) in simulated body fluid (SBF) was investigated. Accordingly, 316L SS samples were electropolished in several electropolishing baths of H₃PO₄ and H₂SO₄ at 2–6 applied volts and 50–110°C for different time intervals. The corrosion behaviour then was studied by means of potentiodynamic polarisation technique and electrochemical impedance spectroscopy in SBF at 37°C. The surface morphology was also investigated by scanning electron microscopy. The results proved that the treated samples had better corrosion resistance than nonpolished one. The highest corrosion resistance was observed for the treated sample at 5?V and 90°C in 10:90 ratio of acidic electrolyte (H₃PO₄:H₂SO₄) for 15?min. Moreover, the corrosion resistances of anodically treated samples were found to be dependent greatly on applied volt, bath temperature, polishing time and phosphoric to sulphuric acids ratio.     

Inhibiting effects of butyl triphenyl phosphonium bromide on corrosion of mild steel in 0.5 M sulphuric acid solution and its adsorption characteristics

Butyl triphenyl phosphonium bromide (BuTPPB) has been evaluated as a corrosion inhibitor for mild steel in 0.5 M H₂SO₄ solutions using galvanostatic polarisation and potentiostatic polarisation measurements. The study was also complemented by infra red (IR) spectroscopy, scanning electron microscopy (SEM) and quantum chemical calculations. Galvanostatic polarisation measurements showed that the presence of BuTPPB in aerated 0.5 M H₂SO₄ solutions decreases corrosion currents to a great extent and the corrosion rate decreases with increasing inhibitor concentration at a constant temperature. At 298K, inhibition efficiency was found to be 94.5% for 10⁻⁷ M BuTPPB which increased to about 99% for the BuTPPB concentration of 10⁻² M. The effect of temperature on the corrosion behaviour of mild steel was studied at five different temperatures ranging from 298 to 338K. The polarisation curves clearly indicate that BuTPPB acts as a mixed type inhibitor. Adsorption of BuTPPB on the mild steel surface follows the Langmuir isotherm.Potentiostatic polarisation measurements showed that passivation was observed only for lower BuTPPB concentrations (10⁻⁵ and 10⁻⁷ mol l⁻¹) for the mild steel in 0.5 M H₂SO₄. IR and SEM investigations also confirmed the adsorption of BuTPPB on the mild steel surface in 0.5 M H₂SO₄ solutions. The molecular parameters obtained using PM3 semi-empirical method, were correlated with the experimentally measured inhibitor efficiencies.     

Improving the corrosion behaviour of powder metallurgical 316L alloy by prepassivation in 20% nitric acid

The electrochemical improvement of PM 316L stainless steels by pre-alloyed powder prepassivation in 20% nitric acid in comparison with as-received specimens has been studied in this work. For comparison purposes a simultaneous study was carried out on similar composition wrought AISI 316L steels. Corrosion resistance was studied using evolution of the corrosion potential vs. time, anodic polarisations curves and Zero Resistance Ammeter technique. Reductions of the corrosion rate (i_corr) were observed in prepassivated specimens in neutral chloride media. Crevice resistance was higher for prepassivated specimens and for higher densities and annealing as post-heat treatments.     

KCl-induced high temperature corrosion of the austenitic Fe-Cr-Ni alloys 304L and Sanicro 28 at 600 °C

The influence of KCl(s) on the high temperature oxidation of the austenitic alloys 304L and Sanicro 28 at 600 °C in O₂ + H₂O environment is reported. 0.10 mg/cm² KCl(s) was added before exposure. The samples are investigated by grazing angle XRD, SEM/EDX, and AES. In the absence of KCl, both alloys show protective behaviour in dry O₂. In O₂ + H₂O environment, alloy 304L suffers local breakaway corrosion while Sanicro 28 still shows protective behaviour. The oxidation of both alloys is strongly accelerated by KCl. KCl reacts with chromium in the normally protective corundum-type oxide, forming K₂CrO₄. This depletes the scale in chromia and leads to the formation of a non-protective, iron-rich scale. The significance of KCl-induced corrosion in real applications is discussed and the oxidation behaviour of the two steels is compared.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

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.     

Pitting of AISI 304L stainless steel coated with nano structured sol–gel alumina coatings in chloride containing acidic environments

Sol–gel coatings were applied on AISI 304L stainless steel and their pitting resistance was evaluated in different concentrations of chloride ions in 0.01 M H₂SO₄ solution. AFM and XRD analyses of the coated surface confirmed the presence of nano structured α-alumina phase in the coating. Anodic polarisation indicated a considerable shift of pitting potential of the substrate in the noble direction after applying coatings. The SEM micrographs of the polarised specimens revealed the presence of relatively less number of pits on the coated surface. EIS analysis demonstrated the occurrence of diffusion process at the coating/metal interfaces in chloride ions presence.     

Formation and breakdown of surface films on magnesium and its alloys in aqueous solutions

The influences of surface films formed by open-circuit exposure to neutral solutions on the corrosion and electrochemical behaviour of pure Mg and Mg alloys have been examined by in situ ellipsometric analysis and electrochemical measurements. Surface films mainly composed of Mg(OH)₂ grew rapidly during open-circuit exposure to 0.1 M NaCl and 0.1 M Na₂SO₄ solutions. These films had protective ability to passivate Mg in the solutions. However, they suffered local breakdown under anodic polarisation. The passive current density decreased and the breakdown potential increased with increasing immersion time and film thickness. Influences of purity and alloying elements on the passivity and its breakdown of Mg have been discussed.     

Fabrication of continuous mesoporous organic–inorganic nanocomposite films for corrosion protection of stainless steel in PEM fuel cells

The organic–inorganic composite film was deposited on the 304 stainless steel as bipolar plate material for proton exchange membrane fuel cells by spin-coating method. As shown by XRD, N₂ adsorption–desorption and TEM, the composite films exhibit ordered mesoporous structures. The corrosion tests in 0.5 M H₂SO₄ system displayed that, compared with 304SS, the composite films made corrosion potential shifted to positive direction by 250–1000 mV (SCE) and corrosion current decreased by 1–3 orders of magnitude. Wherein, the C-50–60% composite film showed the optimal protective performance, its corresponding potentiostatic polarization process was extremely stable in the simulated fuel cells environment.     

The effect of H2S concentration on the corrosion behavior of carbon steel at 90 °C

The electrochemical behavior of SAE-1020 carbon steel in 0.25 M Na₂SO₄ solution containing different concentrations of H₂S at 90 °C was investigated using the methods of weight loss, electrochemical measurements, scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that the corrosion rate of carbon steel increased significantly with the increase of H₂S concentration. H₂S accelerated the corrosion rate of SAE-1020 carbon steel by a promoted hydrogen evolution reaction. Severe corrosion cavities were observed on the carbon steel surface in the solutions containing H₂S due to cementites stripped off from the grain boundary. The loose corrosion products formed on the steel surfaces were composed of mackinawite.     

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.     

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy in 3.5% NaCl solution

The polarization characteristics of Pb-free Sn-8.5Zn-XAg-0.1Al-0.05Ga alloy with varying Ag content were investigated in 3.5% NaCl solution. The value of Ag content i.e X varied from 0.1 wt% to 2 wt%. An increase in the Ag content up to 2 wt% resulted in a progressive increase in the corrosion current density and shifted the corrosion potential (E_corr) towards more active values. These changes were also reflected in the corrosion rate of the solder alloy. However the linear polarization resistance values decreased with increase in the weight content of silver. Increasing the Ag content from 0.1 to 2 wt% did not show a significant improvement in the passivation behaviour of the solder alloy as reflected in the passivation current density (i_p) and critical current density (i_cc) values. XPS and SIMS depth profile results revealed that the oxides of Zn and Sn were present in high concentrations on the outer surface of the solder alloy along with very low concentration of Al₂O₃.