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Ferritic steels with Cr-contents up to 13 wt. % are used as building components in combustion based power plants. These materials are subject to aggressive corrosion caused by the reaction of the steel with highly corrosive gases under high temperatures up to 620°C. Detailed knowledge about corrosion mechanisms regarding the attack of gaseous sulfur dioxide have a significant influence and are not entirely understood. The reaction with SO2 can be seen as two simultaneous processes; oxidation and sulfidation. Especially in the initial state, these processes are more kinetically controlled than thermodynamically. However, a detailed knowledge is a key aspect to understand the complex high temperature corrosion of high alloyed steels with a variety of alloying components ageing under combustion gases with a variety of gas components such as CO2, O2, N2, or SO2/SO3, and to better predict altering of building components and inspection intervals. To get more information about corrosion mechanisms in general and the simultaneous process of oxidation and sulfidation under SO2, initial stadia of the corrosion mechanism have to be studied. In order to minimize and control the free parameters of the corrosion procedure, simplified systems with model alloys and simplified gas compositions are a feasible tool.
The current presentation will deal with the initial stages of high temperature corrosion on Fe-Cr model alloys under SO2+Ar atmospheres. Experiments took place using an infra-red light furnace with higher heating and cooling rates compared to regular tubular furnaces to preserve the high temperature phase distribution. Pure Fe, Fe with 2 wt. % and 13 wt. % Cr were used and aged for time scales between 30s < t < 6h under 0.5% SO2 and 99.5% Ar. Specific positions on each sample were marked with Vickers indentations and the crystal orientations were analyzed using ‘Electron Backscatter Diffraction’ (EBSD) to get the orientation of the ferrite grains in advance. After the corrosion experiment, the same positions were analyzed again using scanning electron microscopy (SEM) and electron microprobe analysis (EMPA) to correlate the crystal orientation with the corrosion product and the elemental distribution. Further, cross sections of the samples were prepared to analyze the phase distribution in depth. Even though Cr and Fe form a solid solution in the crystal lattice, a significant difference in oxide island growth was observed for orientation dependent corrosion on different Fe-Cr alloys.
Hard protective coatings deposited by physical vapour deposition (PVD) methods have been characterised for decades for their corrosion protection capabilities. However, due to growth defects single PVD deposited hard coatings with a thickness below 10 μm are usually not capable to reliably protect steel substrates from corrosion in neutral salt spray (NSS) tests.
In this study, 2.5 μm thick TiN and TiMgN films with Mg-contents between 10 and 35 at.-% were deposited onto 1.3505 steel samples by DC magnetron sputtering. The growth defect concentration on each as-deposited sample was determined by large area high resolution (LAHR) mapping, a confocal microscopy based measurement and evaluation method recently introduced. The NSS test results were thus evaluated not only in relation to the Mg content, but also to the amounts and sizes of growth defects, which markedly reduced random influences. Further characterisations of the TiMgN-coated samples comprised hardness, tribological and electrochemical behaviour of the films as well as the microstructure of selected growth defects. TiMgN with a high Mg content of 35 at.-% showed drastically improved corrosion protection capabilities for steel substrates compared to pure TiN. Coated polished as well as sandblasted samples showed almost no corrosion after 24 h in a NSS test. The defect concentration data further indicated an improved corrosion protection also for TiMgN with lower Mg contents. Cathodical corrosion protection was identified to be the main corrosion protection mechanism. The hardness of TiMgN with 35 at.-% Mg is markedly reduced, nevertheless it showed a good tribological behaviour against e.g. steel. This coating material hence demonstrates a unique combination of wear and corrosion protection properties.
By exposure and electrochemical tests in the laboratory the Cu-effect on corrosion behavior of carbon steel, high-alloyed steels and Ti-alloy can be assessed.
Critical materials specific properties were determined by static exposure and electrochemical tests in an artificial geothermal water with high salinity and low pH, containing Cu. Conclusions were drawn using characteristic potential values.
It could be shown that significant Cu-deposition and -precipitation only occurred in combination with carbon steel. High-alloyed materials (S31603, S31653, S31700, S31703, S31803 and N08904) prevent the disturbing Cu-agglomeration. Therefore, they are suitable to be chosen for future design of the piping system, either in massive or in cladded form, if formation of crevices with non-metallic materials can be excluded.
From the interactions and pitting corrosion point of view, R50400 seems to be most favorable.
Depending on the CO2 generating and the capture process as well as on consecutive purification steps applied, CO2 streams from different emitters may differ in their composition. When CO2 streams with different compositions are fed into a larger pipeline network, there are several aspects that must be considered: i) chemical reactions, such as acid formation, may occur within the joint CO2 stream; ii) there may be a variation of mass flow rate and CO2 stream composition within the pipeline network if the feed-in behavior of different CO2 sources changes with time. Potential impacts of changing CO2 stream compositions and mass flow rates in CCS cluster systems were investigated in the collaborative project "CLUSTER" (see also www.bgr.bund.de/CLUSTER). In this presentation, we focus on the experimental investigations of formation and condensation of strong acids and their impacts on the corrosion of pipeline steels. When SO2, NO2, O2 and H2O are present simultaneously in CO2 streams chemical cross-reactions may occur leading to the formation of strong acids such as sulfuric and nitric acid. To prevent this acid formation the concentration of at least one of these four impurities must be kept very low (e.g., Rütters et al., 2016). At temperatures below the acid dew point temperature, acids will condense, e.g., on pipeline steel surfaces. In turn, these acid condensates may trigger steel corrosion. To better understand the process of acid formation and condensation and its implications for steel corrosion, exposure tests were performed on pipeline steel X70 in dense CO2 with varying SO2, NO2 and O2 concentration under high pressure and at 278 K in an observable autoclave, in which water was added as droplets or as vapor. Further, electrochemical tests were carried out with X70 specimens immersed in 500 mL CO2-saturated synthetic condensate solution or in droplets of the same solution on the specimen’s surface. Depending on impurity concentrations in the CO2 streams, condensates consisting of different relative amounts of nitric and sulfuric acid were formed. In condensates containing both nitric and sulfuric acid, corrosion rates were higher than the sum of those of the individual acids. In addition, corrosion products and forms depended on the condensate composition. Investigations of water droplets on steel surfaces in impurity-containing dense-phase CO2 revealed the diffusion of SO2 and NO2, followed by cross-reactions forming corresponding acids. An increase in droplet size (from 1 to 5 µl) lead to higher corrosion rates. However, in comparison to measurements in bulk solution, corrosion reactions in droplets resulted in thick, high-resistance corrosion products and observed droplet corrosion rates were significantly lower. In addition, the possibility of acid droplet formation and growth in impure liquid CO2 is influenced by the wetting behavior of the acid droplet on the steel surface. Thus, the contact angle between a water droplet and the surface steel specimens in a CO2 atmosphere was investigated in a high pressure view cell following the sessile drop method. The contact angle wasand found to be larger at higher CO2 pressures (studied from 5 to 20 MPa) and at higher temperatures (e.g. 278 K to 333 K). Further, measured contact angles were larger on rough than on smooth metal surfaces. In addition, acid formation reduced the contact angle, i.e. lead to better wetting, thereby stimulating condensation that was followed by a corrosion process. These detailed insights on the complex interplay of acid formation, condensation, wetting behavior and corrosion allow a better assessment of material suitability for pipeline transportation of impure CO2 streams