KCl-Induced High Temperature Corrosion of Austenitic Stainless Steel 304L – The Influence of SO2

Journal article, 2011

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. Keywords: Oxidation, Alkali, Breakaway Corrosion, 304L, Chromate, Sulphur