Ingenieurwissenschaften und zugeordnete Tätigkeiten
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Real Time Imaging of Deuterium in a Duplex Stainless Steel Microstructure by Time-of-Flight SIMS
(2016)
For more than one century, hydrogen assisted degradation of metallic microstructures has been identified as origin for severe technical component failures but the mechanisms behind have not yet been completely understood so far. Any in-situ observation of hydrogen transport phenomena in microstructures will provide more details for further elucidation of these degradation mechanisms. A novel experiment is presented which is designed to elucidate the permeation behaviour of deuterium in a microstructure of duplex stainless steel (DSS). A hydrogen permeation cell within a TOF-SIMS instrument enables electrochemical charging with deuterium through the inner surface of the cell made from DSS. The outer surface of the DSS permeation cell exposed to the vacuum has been imaged by TOF-SIMS vs. increasing time of charging with subsequent chemometric treatment of image data. This in-situ experiment showed evidently that deuterium is permeating much faster through the ferrite phase than through the austenite phase. Moreover, a direct proof for deuterium enrichment at the austenite-ferrite interface has been found.
CO2 streams captured from power stations or industrial plants may contain impurities that impact the consecutive steps of the CO2 capture and storage (CCS) chain. As the basis for an optimization of CO2 purity over the whole CCS chain, impacts of different impurities were investigated at key steps including studies on (i) corrosion of metallic materials in CO2 streams and brine, (ii) fluid and interfacial properties as a function of pressure, temperature and CO2 stream composition and their implications for CO2 transport, injection and geological storage, (iii) costs of different pipeline design options, (iv) geochemical alterations at typical reservoir conditions and their implications for geomechanical rock properties. Major findings are synthesized for two exemplary single source-single sink CCS chain scenarios involving CO2 stream compositions typical for pre-combustion capture and oxyfuel combustion. Recommendations for material selection for compression, transport and injection were derived for various CO2 stream compositions. To reliably control corrosion, a limitation of water contents to 50 ppmv is recommended for pipeline transportation of all CO2 streams. At geological storage conditions, the presence of either O2, NOx or SO2 only weakly affected fluid-mineral/rock interactions that still impacted geomechanical rock properties.
Manganese alloyed stainless steels represent a cost-effective alternative to conventional CrNi- stainless steels due to strong fl uctuations of the market prices for nickel seen during the last years. In CrMnNi steels, nickel is partially replaced by lower-cost manganese and small amounts of nitrogen for stabilization of the austenitic phase. This also brings benefi ts regarding the mechanical properties, as it results in an increased material strength. Laser beam welding of such materials was investigated for direct comparison with Standard CrNi steels. Main emphasis was laid on fi nding adequate process parameters to achieve a stable welding process and obtain a good weld quality. Two different laser sources, a 4.4 kW Nd:YAG and a 5 kW CO2 laser, were used to weld 1.5 mm stainless steel sheets in continuous wave mode. A high-Mn austenitic (1.4376) and a lean duplex (1.4162) steel, as well as the standard austenitic (1.4301) and duplex (1.4362) grades were selected as test materials. Both butt and lap joint confi gurations were studied. Experiments were carried out systematically, varying the welding speed, laser power and focal point position in order to determine adequate process windows. The infl uence of the shielding gas type and fl ow rate on the process stability and the weld quality were investigated. The effects of weld edge preparation on the weld appearance and quality levels attained were also examined. The obtained welded joints were subjected to radiographic tests for detection of internal imperfections. Also a metallurgical characterization of the samples regarding the resulting phase composition or balance and hardness depending on the welding process parameters was conducted. Furthermore, tensile and potentiodynamic tests were performed to evaluate the mechanical and corrosion properties, respectively. The results provide an insight into the advantages and limitations of the laser beam welding process for joining high-manganese alloyed stainless steels. Conditions for the production of defect-free and corrosion-resistant welds having good mechanical properties could be determined.
Adhesion and corrosive delamination of epoxy films on chemically etched ZnMgAl-alloy coatings
(2016)
The effect of alkaline and acidic pretreatment steps on the surface chemical
composition and adhesion properties of ZnMgAl-alloy coated steel was
investigated by means of spectroscopic methods, scanning Kelvin probe (SKP)
and peel test measurements.The spectroscopic results indicate that the surface
film composition can be adjusted by the wet-chemical treatment. To study the
corresponding surface adhesive properties, the samples were coated with an
epoxy amine adhesive. Peel tests under humid conditions indicated an
increased interaction between the acidic pre-treated surface and the adhesive.
The results of the SKP analysis show that the acidic cleaned substrates have the
highest resistance to delamination, which can be explained by the shift of the
interfacial electrode potential.
Properties of pipe steels for CCS (carbon capture and storage) technology require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). The influence of austenitzing in heat treatment routines of two different injection pipe Steels (1.4034, X46Cr13 and 1.4021, X20Cr13) was evaluated. Steel coupons were austenitized at different temperatures (900- 1050 °C) for different lengths of time (30-90 min) before quenching and annealing prior to long term corrosion experiments (60°C, 100 bar, artificial brine close to a CCS-site in the Northern German Basin, Germany). In general, fewer pits are found on X46Cr13. Comparing steels with 13% chromium each the higher carbon content of X46Cr13 (0.46% C) results in a lower number of pits compared to X20Cr13 (0.20% C). It is found that neither the carbon content of the steels nor austenitizing temperature has much influence, but local corrosion behaviour is most susceptible towards austenitzing time.
Properties of pipe steels for CCS (carbon capture and storage) technology require resistance against the corrosive environment of a potential CCS-site (heat, pressure, salinity of the aquifer, CO2-partial pressure). The influence of austenitzing in heat treatment routines of two different injection pipe steels (1.4034, X46Cr13 and 1.4021, X20Cr13) was evaluated. Steel coupons were austenitized at different temperatures (900-1050 °C) for different lengths of time (30-90 min) before quenching and annealing prior to long term corrosion experiments (60°C, 100 bar, artificial brine close to a CCS-site in the Northern German Basin, Germany). In general, fewer pits are found on X46Cr13. Comparing steels with 13% chromium each the higher carbon content of X46Cr13 (0.46% C) results in a lower number of pits compared to X20Cr13 (0.20% C). It is found that neither the carbon content of the steels nor austenitizing temperature has much influence, but local corrosion behaviour is most susceptible towards austenitzing time.
Ferritic-martensitic high temperature alloys are used as building components for different power plant technologies. Depending on the type of fuel, the used power plant materials are exposed to different temperatures and reactive atmospheres containing e.g. CO2, O2, or SO2. Despite the sulfur chemistry is commonly present as an impurity in fossil or bio fuels; its role in high temperature corrosion is not entirely understood. During high temperature corrosion, high-alloyed steels often show sulfur precipitates with the ignoble alloy component(s) along grain boundaries within the base material. Sulfur precipitates are known to seriously influence the mechanical properties of the building component. In the case of VM12 and T92 steels, sulfur phases penetrate the base material along grain boundaries during the corrosion under oxyfuel atmosphere up to 20 µm within the first 960h (Fig. 1a). Figure 1a shows the oxide scale and (Cr, Mn, Fe)xSy grain boundary precipitates in the base material for a T92 steel aged for 960h under oxyfuel atmosphere. Figure 1b shows a thin oxide scale with nodules and also sulfur precipitates of (Fe, Cr)xSy along grain boundaries of the base material for a Fe13Cr model alloy aged for 24h under SO2 atmospheres. After 24h, sulfur precipitates already reached a depth of ca. 15 µm.
The present work shows the corrosion behavior of Fe-Cr model alloys with Cr-contents similar to technical steels up to 13 wt%, aged under oxyfuel (27H2O/60CO2/1SO2/10N2/2O2) and SO2 atmospheres in the temperature range of 550 °C < T < 700 °C and for different time scales between 24 h < t < 960 h. During aging, the reactive gases were added when the experimental temperature was reached. To focus on the reaction of the intended elements Fe, Cr, S, and O, model alloys of high purity are used. Transport depths of sulfur and the nucleation of the precipitates are discussed for both, model alloys and technical steels.
In Kraftwerkstechnologien verwendete ferritische Fe-Cr-Stähle sind verschiedensten Temperaturen, Prozessdrücken und aggressiven, zum Teil schwefelhaltigen Verbrennungsgasen ausgesetzt, die zu Korrosion führen. Noch ungeklärt ist die Rolle der entstehenden Sulfide in der schützenden Oxidschicht und deren Auswirkung auf die Lebensdauer der Bauteile. Unsere Arbeit zeigt Korrosionsmechanismen ausgewählter Fe-Cr-Modelllegierungen unter Ar-SO2 Atmosphäre für verschiedene Zeitskalen. Der Focus dabei liegt auf Kurzzeitexperimenten (12h ≤ t ≤ 250h), um die initialen Stadien der Schwefelkorrosion zu untersuchen.