The role of two oxygen sources, air and water vapor, in the initiation of KCl-induced high-temperature corrosion was addressed with three different commercial alloys typically used in power plants. The focus was on the initiation of the corrosion reaction, so an exposure time of 120 min at 540°C was used under flowing conditions. The possible selectivity of oxygen in the corrosion reaction was studied by using two different stable oxygen isotopes, 16O in air and 18O in water vapor, and identifying the isotopes after the reaction with of time-of-flight secondary ion mass spectrometry (ToF-SIMS). In addition, the surface morphologies were imaged with scanning electron microscopy and energy dispersive x-ray spectroscopy (SEM-EDX) and the depth profiles mapped with x-ray photoelectron spectroscopy (XPS). Despite the chemical composition of the tested alloys, the alloy surface appears to favor a direct reaction with oxygen from water vapor, when available. On the contrary, the oxygen from air is more involved in reaction(s) forming potassium chromate (K2CrO4). The formation of K2CrO4 provides further evidence of the role of potassium in the initiation of KCl-induced high-temperature corrosion.

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