T. Olszewski

Scale formation mechanisms of martensitic steels in high CO2/H2O-containing gases simulating oxyfuel environments

Abstract In oxyfuel power plants, metallic components will be exposed to service environments containing high amounts of CO2 and water vapour. Therefore, the oxidation behaviour of a number of martensitic 9–12%Cr steels in a model gas mixture containing 70% CO2–30% H2O was studied in the temperature range 550–700°C. The results were compared with the behaviour in air, Ar–CO2 and Ar–H2O. It was found that in the CO2- and/or H2O-rich gases, the mentioned steels tended to form iron-rich oxide scales with significantly higher growth rates than the Cr-rich surface scales formed during air exposure. The iron-rich scales were formed as a result of a decreased flux of chromium in the bulk alloy toward the surface because of enhanced internal oxidation of chromium in the H2O-containing gases and carbide formation in the CO2-rich gases. Additionally, the presence of water vapour in the exposure atmosphere led to buckling of the outer haematite layer, apparently as a result of compressive oxide growth stresses. The Fe-base oxide scales formed in CO2(–H2O)-rich gases appeared to be permeable to CO2 molecules resulting in substantial carburization of the steel.

The oxidation behaviour of the 9 % Cr steel P92in CO2- and H2O-rich gases relevant to oxyfuel environments

Abstract In oxyfuel plants metallic heat exchanging components will be subjected to service environments containing high amounts of CO2 and water vapour. In the present paper, the oxidation behaviour of the ferritic/martensitic 9 % Cr steel P92 was studied in a model gas mixture containing 70 % CO2-30 % H2O in the temperature range 550 – 650 °C. The results were compared with the behaviour in air, Ar–CO2 and Ar–H2O. In the CO2- and/or H2O-rich gases, the steel formed iron-rich oxide scales which possess substantially higher growth rates than the Cr-rich surface scales formed during air exposure. The iron-rich oxide scales are formed as a result of a decreased flux of chromium in the bulk alloy toward the surface. This is the result of enhanced internal oxidation of chromium in the H2O-containing gases and carburisation in the CO2 gases. The oxide scales allow molecular transport of CO2 towards the metallic surface, resulting in carburisation of the alloy. The presence of water vapour induced buckling in the outer haematite layer, apparently as a result of compressive oxide growth stresses. Buckling did not occur in the H2O-free gas. This has been discussed in terms of the potential for H2O to increase growth stresses and accelerate crack propagation. The oxidation rates in CO2–H2O do not seem to be higher than those observed in flue gases of conventional fossil fuel fired power plants.

Oxidation of Metallic Materials in Simulated CO2/H2O-Rich Service Environments Relevant to an Oxyfuel Plant

In the present study the oxidation behaviour of a number of candidate alloys for heat exchanging components was investigated in model gas mixtures containing high amounts of CO2 and/or water vapour in the temperature range 550-700°C up to exposure times of 1000 h. During exposure in Ar/CO2 and Ar/CO2/H2O base gas mixtures at 550-650°C the oxidation rates and scale compositions of martensitic 9-12%Cr steels were similar to those previously observed in steam environments. Thin and protective Cr-rich oxide scales which are commonly found during air oxidation was observed locally on the specimens surfaces after oxidation in Ar-(1-3%)O2-CO2. The tendency for protective chromia base scale formation increased when 3% oxygen was added, especially for the 12%Cr steel. When iron base oxide scales were formed on the metal surface, the martensitic steels tended to exhibit carburisation whereby the extent was reduced by increasing the water vapour and oxygen contents. All three studied austenitic alloys exhibited very slow scale growth rates at 550°C, however, at and above 600°C the steels with lower Cr content started to form two-layered iron rich surface oxide scales whereby the outer oxide was prone to spallation upon thermal cycling. The high-Cr austenitic steel 310N and the nickel base alloy 617 formed very thin, Cr-rich oxide scales at all used test temperatures and atmospheres. For those two materials the oxidation behaviour in gases containing water vapour in combination with intentionally added oxygen was affected by formation of volatile chromium oxyhydroxide.