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To investigate early stage corrosion processes of stainless steel 1.4301 taking place during the biofilm formation of the organism Shewanella putrefaciens electrochemical impedance spectroscopy (EIS) in a multielectrode approach has been used. The multielectrode array consisted of up to 25 electrically isolated electrodes made of stainless steel wires of diameters ranging from 100 µm to 500 µm. They were connected to a multichannel microelectrode analyzer (MMA) electrically coupled through zero resistance ammeters. Current flow between electrodes in the array as well as changes in impedance of individual electrodes over time were recorded and analyzed with respect to the onset of localized corrosion and biofilm formation. The results were complemented by optical microscopy, SEM and AFM images which were taken immediately after the respective experiment. To verify that the multielectrode arrays correctly indicated the initial stages of the corrosion process and of biofilm formation they were introduced in a flow cell reaction vessel containing test specimens made from stainless steel 1.4301, which were checked regularly for signs of localized corrosion and biofilms. Preceding results with the multielectrode array in solutions containing high amounts of chloride ions and hydrogen peroxide at low pH also showed that it is possible with the MMA to monitor individual electrodes becoming local anodes as local corrosion set in, while the remaining electrodes predominantly acted as cathodes.
Nickel-free, nitrogen alloyed austenitic stainless-steels, with about 19 wt.-% Mn and 0,8 wt. % N, are an interesting alternative to classic CrNi austenitic stainless steels due to their superior mechanical properties (Rm > 900 MPa, A5 > 50 %, Av > 350 J) in the solution annealed condition. The formation of chromium-rich nitrides during suboptimal heat treatment, processing or application leads to an inhomogeneous distribution of alloying elements in the microstructure, which reduces the corrosion resistance. Consequently, an accurate knowledge of the sensitization behavior is indispensable for the use of nickel-free, high-nitrogen austenitic stainless steels. The relationship between artificial aging, phase formation and corrosion resistance was investigated on the alloys X8CrMnN18-19 (1.3815) and X8CrMnMoN18-19-2 (1.4456), both alloyed with 0,8 wt.-% Nitrogen, in the present work. The microstructural evolution was studied by LM and SEM while the corrosion resistance was characterized with the electrochemical potentiodynamic reactivation (EPR) and the KorroPad indicator-test. Both alloys showed increased corrosion susceptibility within critical aging parameters. Finally, a sensitization diagram was described successfully for both alloys showing the positive effect of molybdenum.
Hardness and pitting corrosion resistance are the major quality criteria of cutlery. Both are achieved by the heat treatment (austenitization, quenching and tempering) of the normally used martensitic stainless steels. The established quality control method regarding the pitting corrosion resistance is an alternating immersion test in 1 % NaCl solution at 60 °C according to DIN EN ISO 8442. This standard test shows a high deviation, which limits any optimization of the heat treatment process. New approaches for corrosion testing of martensitic stainless-steels were developed and used in the last years to connect the weak pitting corrosion resistance of martensitic stainless-steels with the phenomenon of chromium depletion. The tempering temperatures used in the industrial heat treatment of cutlery are too low to explain the appearance of chromium depletion. For this reason, a systematic investigation of three heat treatment parameters (austenitization time, cooling speed and tempering temperature) were performed on the martensitic stainless-steels X50CrMoV15 (1.4116) to detect their contribution to chromium depletion. The electrochemical potentiodynamic reactivation (EPR), which is very sensitive to any change of the microstructure, was used to quantify the degree of chromium depletion. The KorroPad indicator-test was applied to correlate low pitting corrosion resistance to the presence of chromium depletion. The results of all investigations allow conclusions about the very small process window, which is necessary to achieve cutlery with high pitting corrosion resistance.
The KorroPad indicator test was invented at the Federal Institute for Materials Research and Testing to detect stainless-steel surfaces susceptible to pitting corrosion. The KorroPad indicator test is thus an interesting alternative for manufacturers, processors, users and researchers to time consuming exposition experiments and complex electrochemical investigations, which are normally used to reveal surface-related processing errors resulting in reduced pitting corrosion resistance. Furthermore, the KorroPad indicator test can be used to visualize alloy- and microstructure-related factors causing susceptibility to pitting corrosion. The detection limit of the KorroPad indicator test was characterized in this work using reference alloys with different chromium content (5 % to 18 %). The alloy-specific detection limit was shifted successfully to higher chromium content by increasing the concentrations of NaCl and K3[Fe(CN)6]. The modified KorroPads can now be used to establish an alloy-specific quality control regarding the pitting corrosion resistance of different stainless steel grades.
In context of CLUSTER project, impacts of impurities (SO2, NO2, O2, CO, H2S, H2, N2, Ar and H2O) in CO2 streams captured from different sources in a regional cluster on transport, injection and storage were investigated. Corrosion studies of oxidizing, reductive or mixed atmospheres towards transport pipeline steel X70 were carried out applying high pressure (10 MPa) at low temperatures (278 K or 313 K).
Microbiologically influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms, either chemically (formation of hydrogen sulfide) or electrically (direct electron uptake). Methanogenetic Archaea are also known to be involved in iron corrosion, forming a multi-species biofilm on corroding metallic structures. However, mechanistic details and kinetics of the overall process in methanogen-induced MIC are poorly understood.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons (Fe → Fe²⁺ + 2e⁻ ; E° = 0.47 V) in electrical contact through surface attachment. Also methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO₃⁻ + 5H⁺ → 4FeCO₃ + CH₄ + 3H₂O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO₃ precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
To investigate the corrosive potential of methanogens, we studied strains isolated from marine sediments (Methanococcus maripaludis 14266, 2067, Methanobacterium-affiliated strain IM1), crude oil tanks (Methanococcus maripaludis Mic1c10, KA1) and the oral cavity (Methanobrevibacter oralis) in a closed (batch) culture, and in a sand-packed flow-through cell with pH control and simulation of a fluctuating environment. Results indicate that the rates of iron corrosion due to coupled methanogenesis (up to 0.3 mm/yr) are comparable to that caused by SRM. Surface analyses of the metal showed severe pitting. Such knowledge and deeper understanding also from an electrokinetic point of view may not only provide further models in microbial electrophysiology, but also contribute to mitigation strategies in MIC.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.