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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.
Ferritic steels with Cr-contents up to 13 wt. % are used as heat exchanger or boiler tube materials 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 650°C. The early stages of corrosion and sulfidation especially and the influence of the Cr-content in the alloy are thereby not understood but of fundamental interest.
Our work shows corrosion mechanisms and presents corrosion models for Fe and different Fe-Cr-alloys under pure SO2 und SO2+O2 atmospheres for different time scales. Modell alloys of high purity are used to focus on the reaction of the intended elements: Fe, Cr, S, and O. Long-time experiments (≥12h) took place in tube furnaces and short-time experiments (≥5min) in a special designed light furnace. Heating and cooling took place under inert atmosphere. The reactive gases were added not until the experimental temperature was reached. Samples were analyzed using high resolution synchrotron X-ray diffraction using a micro focus setup and electron microscopy including FIB.
Many earlier studies on corrosion and sulfidation on iron based alloys show a higher corrosion rate and material loss when sulfur was present in the atmosphere. In contrast, later studies propose an inhibiting effect of sulfur containing atmospheres. On the one side, most likely due to the formation of a protective layer of Mx(SO4)y -phases at the scale-gas interface. On the other side, a very recent study proposes the theory that MxSy-phases limit the further diffusion of elements. Up to now, no Mx(SO4)y –phases were detected in our samples, but sulfide phases nucleated within the oxide phases. For pure Fe our samples show FeS at the scale-metal interface working as a diffusion barrier for Fe-Cations from the base material in to the oxide scale. The above lying spalled off oxide-sulfide scale shows a wide area of small voids and accumulations of FeS-Crystals at the bottom. Under the main oxide scale a second generation of oxide-sulfide scale starts to form. For the Fe-Cr-alloys the inner oxide scale only shows FeS- and CrS-phases surrounded by hollow space. The here presented study will explain and discuss a new growth model for the shown phenomenon.
Ferritic alloys containing Cr form Cr5S6 precipitates along grain boundaries in hot SO2 environment. Grain boundary precipitates may influence the steel’s mechanical behavior. Cr5S6 precipitates were reconstructed three-dimensionally using FIB tomography analysis to determine the volume, number, and penetration depth. The volume growth of Cr5S6 precipitates increased only for the initial aging time of 3 h but became constant after 6 h. The number of precipitates increased linearly.
Insights into early damage mechanisms during high-temperature gas corrosion provide important aspects for the prediction of the long-term stability of hightemperature materials exposed to a hot and corrosive environment. The current work presents a real time study concerning the combined oxidation and sulfidation of ferritic model alloys in a hot SO2 containing atmosphere using energy dispersive X-ray diffraction. The applied high temperature reactor allows the transmittance of high energetic X-rays in order to collect X-ray diffraction pattern of the sample surface in situ during the reaction with the reactive environment. The results revealed that the first phases crystallizing on iron with 2 wt% chromium and with 9 wt% chromium are oxides. The aging experiments at T = 650° C with 0.5% SO2 and 99.5% Ar were followed in situ and caused an external mixed oxide-sulfide layer on top of iron with 2 wt% chromium. On the higher alloyed material the external scale consists of iron oxides and the inner scale of mixed (Fe,Cr)-oxides and chromium-sulfides. The oxide content continuously increases parallel to an increase of the sulfide amount. Thus, the initially formed (Fe,Cr)-oxides do not have a protective character and support the transport of sulfur through the growing oxide scale.