The influence of KCl, NaCl and CaCl 2 on the oxidation of 304-type (Fe18Cr10Ni) stainless steel at 600°C in 5 %O 2 ? 40 %H 2 O was investigated. Prior to exposure, a small amount of the preferred salt (cation equivalent: 1.35 lmol/cm 2 ) was deposited on the samples. Exposure time was 1-168 h. The oxidized samples were analyzed by SEM/EDX, XRD, FIB and IC. The presence of KCl and NaCl strongly accelerates high temperature corrosion of 304L. Corrosion attack is initiated by the formation of alkali chromate through the reaction of alkali with the protective oxide. Chromate formation is a sink for chromium in the oxide and leads to a loss of its protective properties. Subsequently a rapidly growing scale forms, consisting of an outer hematite layer with chromate particles on top and an inner spinel oxide layer. In contrast to NaCl and KCl, CaCl 2 is not very corrosive. At temperature, CaCl 2 is rapidly converted to CaO. Small amounts of CaCrO 4 form where CaO is in direct contact with the scale. CaO also reacts with the scale to form Ca 2 Fe 2 O 5 .

The effect of SO2(g) on the initial oxidation of the stainless-steel 304L, sprayed with 0.1 mg/cm2 KCl and exposed in 5% O2 and 40% H2O at 600 °C, was investigated. In the absence of SO2(g), KCl accelerates the corrosion attack by the formation of K2CrO4. The reaction with KCl depletes the oxide in chromium and converts it into an iron-rich, poorly protective oxide. When SO2(g) was introduced to the gas flow, KCl rapidly transformed into K2SO4. In contrast to KCl, K2SO4 does not form K2CrO4. Hence, it does not accelerate the corrosion rate. Although the conversion of KCl to K2SO4 is fast, the corrosion rate of KCl samples exposed in the presence of SO2(g) is higher than samples exposed in the presence of K2SO4. It is therefore suggested that small amounts of unreacted KCl react initially with the protective oxide, forming K2CrO4, which depletes the oxide in chromium. However, because of the presence of SO2(g), K2CrO4 immediately reacts with SO2(g) to form K2SO4. This study shows that the initial stages of the corrosion attack are of great importance. The initial complex interactions between the flue gas, deposit, and oxide scale affect the future corrosion resistance of the steel.

Breakaway oxidation of alloy 304L at 600°C was studied in four environments (O 2

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The effect of SO2 on the oxidation of alloy 304L in O2+H2O and O2+H2O+KCl environment has been investigated at 600°C. Exposure time was 1-168 hours. The exposed samples were analyzed by SEM/EDX, XRD and IC. In dry O2, a protective and chromium-rich corundum-type oxide forms. In the presence of H2O(g), chromium is volatilized in the form of CrO2(OH)2(g). The corresponding chromium depletion of the protective oxide triggers a partial loss of protective properties resulting in the formation of oxide islands on the alloy grain centers. The oxide islands consist of an outward growing hematite layer and an inward growing FeCrNi spinel layer. By coating the samples with KCl the chromia depletion of the protective oxide dramatically increases due to the formation of K2CrO4. This leads to breakaway corrosion, a rapidly growing scale forming all over the surface. The resulting thick scale has a similar structure as the oxide islands formed in the absence of KCl. The addition of 300 ppm SO2 to the O2+H2O and O2+H2O+KCl environments results in a drastic reduction of corrosion rate. In O2+H2O environment the effect of SO2 is attributed to the formation of a thin sulphate film on the oxide surface that impedes chromium volatilization and decreases the rate of oxygen reduction on the oxide surface. In O2+H2O+KCl environment the corrosion mitigating effect of SO2 is mainly attributed to the rapid conversion of KCl to K2SO4. In contrast to KCl, K2SO4 does not deplete the protective oxide in chromium by forming K2CrO4.