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The Stolt Rotterdam tanker ship, filled with nitric acid, was unloading at the Krefeld-Uerdingen terminal on the Rhine River in November 2001. Nitric acid ran out of the stainless steel tanks into the ship's hull and damaged the structural steel. The ship then caught fire and sank at the terminal. Large quantities of nitrogen oxides were emitted, which drifted towards a residential area. Additionally, a mixture of acid and water was introduced into the Rhine River. The area became hazardous to people and the natural environment; however, the imminent danger for the residents and the environment was reduced because of the protective measures against pollution and the good teamwork between local authorities, fire brigades and the Bayer AG company. The acid was drained off of the ship using a controlled discharge of the acid into the river. Through the use of this measure, the ship was salvaged, limiting the pollution to the area and removing the health hazards to the people and the environment. After the ship was salvaged, the river police, along with assistance from the BAM Federal Institute for Materials Research and Testing, impounded the ship and selected corroded parts for further examination. Some of these components have been examined in detail by the BAM. These material investigations contributed to the elucidation of the origin of the leak in the floor panel. The cause of damage was deemed to be a result of a construction flaw at the enamelled valve on the load and discharge pipes.
The results from the comparative corrosion testing using the original structural steel and 60% acid revealed that the valves began to leak at least 8 h prior to the incident at the terminal.
The safety assessment of railway axles is based on a two-stage approach: fatigue strength design and regular inspections which, in terms of a general safety philosophy refer to safe-life and damage tolerance concepts. Starting with a recent failure case, a broken axle of a German high speed train, a discussion is presented on issues of both safety levels. These include ideas for finite life design, the treatment of in-service effects on the fatigue strength due to flying ballast damage and corrosion pits, the effect of corrosion on fatigue crack initiation and propagation, potential effects of non-metallic inclusions in steels, the way to detect them by quality control measures and reliability aspects of non-destructive testing with respect to the detection of fatigue cracks. Proposals are made how the safety level could be further improved.
Corrosion resistance of duplex stainless steel (SS) (UNS S32101) and super austenitic SS (UNS NO8031) (Alloy 31) was investigated in crevice conditions in a saline brine. Rubber was used to form a metal/non-metal-crevice confguration. UNS NO8031 did not exhibit any signs of pitting corrosion even by applying potentials much more positive than the corrosion potential.
Condensates from the gas stream in simulated CO2 transport pipelines have been identified during the experiments in the laboratory. Because of their acidic origin the corrosion resistance of pipeline steels used for CCS (carbon capture and storage) technology might be limited. Over the last years it has become clear that the amount of water and acid building constituents in the CO2 stream has to be controlled very well. In this work, condensates formed in experiments using gaseous CO2 containing high amounts of water, NO2 and SO2 were analyzed, replicated, and used for extensive electrochemical experiments. These highly acidic condensates were enriched with CO2 and then applied to characteristic steels planned to use in the CCS transport chain. Even high alloy steels are susceptible to localized corrosion under these conditions. The results implicate that condensation of aggressive acid droplets has to be avoided or the locations where condensation takes place have to be controlled extensively.
The process chain for Carbon Capture and Sequestration (CCS) includes tubing for injection of CO2 into saline aquifers. The compressed CO2 is likely to contain specific impurities; small concentrations of SO2 and NO2 in combination with oxygen and humidity are most harmful. In addition, CO2 saturated brine is supposed to rise in the well when the injection process is interrupted. The material selection has to ensure that neither CO2 nor brine or a combination of both will leak out of the inner tubing. In this comprehensive paper the investigated materials range from low-alloy steels and 13% Cr steels up to high-alloy materials. Electrochemical tests as well as long term exposure tests were performed in CO2, in brine and combination of both; pressure was up to 100 bar, temperature up to 60 °C. Whereas the CO2 stream itself can be handled using low alloy steels, combinations of CO2 and brine require more resistant materials to control the strong tendency to pitting corrosion. The corrosion behavior of heat-treated steels depends on factors such as microstructure and carbon content. For different sections of the injection tube, appropriate materials should be used to guarantee safety and consider cost effectiveness.
Stainless steel AISI 304 surfaces were studied after a mild anodic polarization for oxide growth in the presence and absence of two derivatives of vitamin B2 (riboflavin and flavin mononucleotide) that can be secreted by metal‐reducing bacteria and act as a chelating agent for iron species. The alterations in oxide chemistry were studied by means of surface‐sensitive techniques such as X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry analysis. The complementary electrochemical characterization revealed a preferential growth of an oxide/hydroxide iron‐rich film that is responsible for an altered pit initiation and nucleation behavior. These findings suggest that as the corrosion behavior is determined by the interplay of the chemical and electronic properties, only a mild anodic polarization in the presence of redox‐active molecules is able to alter the chemical and electronic structure of the passive film formed on stainless steel AISI 304. This helps to achieve a profound understanding of the mechanisms of microbially influenced corrosion (MIC) and especially the possible effects of the redox‐active biomolecules, as they may play an important role in the corrosion susceptibility of stainless steel surfaces.
This work presents the determination of the corrosion characteristics of CrCoNi (medium entropy alloy) and CrMnFeCoNi (high entropy alloy) in 0.1 M NaCl and 0.1 M H2SO4. The morphology and chemical composition of the oxide layers formed on CrCoNi and CrMnFeCoNi were comparatively analyzed by scanning Kelvin probe microscopy (SKPFM) and scanning electron microscopy (SEM) and supported with chemical analysis by means of inductively coupled plasma mass spectrometry (ICP-MS) and X-Ray photoelectron spectroscopy (XPS). The analysis of the 3p core level peaks showed that the oxide layer (native and after anodic passivation) on CrCoNi consisted mainly of Cr oxides, while the oxide layer on CrMnFeCoNi was primarily composed of a mixture of Cr and Fe oxides. In addition, XPS was utilized to assess the oxide layer thicknesses. These results were compared to the thicknesses obtained by means of electrochemical impedance spectroscopy (EIS), with both approaches yielding values up to about 4 nm depending on the electrolyte and the alloy. Cyclic polarization measurements indicated superior corrosion resistance of CrCoNi in both aqueous environments compared to CrMnFeCoNi, as well as to AISI 304 stainless steel.
Multi-principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER-onset detection, and quantitative chemical analysis with inductively coupled-mass spectrometry (ICP-MS) and ultraviolet visible light (UV-Vis) spectroscopy to elucidate metal dissolution processes. In-situ electrochemical atomic force microscopy (EC-AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors.
Single-pass solid-state laser welding of plates in the thickness range of 10 to 20 mm became possible with the invention of the fibre laser. This new technique provides excellent beam quality at powers as high as 20 kW or more, and has proved applicable in several industrial applications. By replacing conventional methods with the fibre laser, it is possible to avoid multiple-pass welding that requires time-consuming bevelling. The high energy density of the fibre laser beam also reduces the heat input and consequently the distortion. However, the rapid solidification and cooling associated with laser welding can cause imbalance of the microstructure of duplex stainless steel weldments, where excessively high ferrite contents may reduce the corrosion resistance and the ductility of the material. The solution is normally to add nickel-based filler wire and to increase the heat input. By using a hybrid welding process where the laser beam and the gas metal arc (GMA) process act in a common process zone, filler metal can be added to the molten pool at higher heat input and at the same time, higher welding speed and deeper penetration can be achieved. In this work, 13.5 mm thick 2205 (EN 1.4462, UNS S31803) was fibre laser-GMA hybrid welded in a single-pass using 14 kW of laser power and ISO 22 9 3 N L as filler wire for the GMA process. The resulting welds were free from defects, with smooth surfaces and full penetration. The investigation examines the weld metal microstructure and the effect on corrosion resistance and mechanical properties. The option to add nickel foil, when hybrid welding, was also investigated, as comparison, and the effect on austenite formation was evaluated.
In lightweight car body shell mass production, due to requirements on vehicle weight reduction and carbon dioxide emissions, joining of advanced high strength steels (AHSS) with different joining procedures and especially hybrid bonding techniques is becoming more and more important. One of these hybrid bonding techniques is the combination of resistance spot welding and adhesive bonding called weldbonding. One of the important advantages of weldbonded joints in comparison to resistance spot welded joints are the enhanced mechanical properties. To guarantee sufficiently high quality conditions regarding the strength of the weldbonded joints, the influences of the applied adhesive systems and of different base metal combinations are studied. This is carried out for both non-corrosive and corrosive environments and for the choice of different joining parameters settings. In particular, the mechanical behaviour of the weldbonded joints is investigated under quasi-static, impact and fatigue loads. Furthermore, the energy absorption of the weldbonded joints for both non-corrosive and corrosive environments is studied. It is shown that the weldbonded joints possess higher mechanical strengths in all load cases (quasi-static, impact and fatigue). Corrosive attack affects weldbonded joints, and the quasi-static strength is reduced. Resistance spot welded joints are not affected by the corrosive attack, but even after several weeks of corrosive attack, the quasi-static strength of weldbonded joints remains higher than that of resistance spot welded joints.