Hot corrosion of materials: Fundamental studies

Hot corrosion is the accelerated oxidation of materials at elevated temperatures induced by a thin film of fused salt deposit. Because of its high thermodynamic stability in the mutual presence of sodium and sulfur impurities in an oxidizing gas, Na₂SO₄ is often found to be the dominant salt in the deposit. The corrosive oxyanion-fused salts are usually ionically conducting electrolytes that exhibit an acid/base chemistry, so that hot corrosion must occur by an electrochemical mechanism that may involve fluxing of the protective oxides. With the aid of high-temperature reference electrodes to quantify an acid/base scale, the solubilities for various metal oxides in fused Na₂SO₄ have been measured, and these show remarkable agreement with the theoretical expectations from the thermodynamic phase stability diagrams for the relevant Na-Metal-S-O systems. The solubilities of several oxides infused Na₂SO₄-NaVO₃ salt solutions have also been measured and modeled. Such information is important both in evaluating the corrosion resistance of materials and in interpreting any oxide fluxing/reprecipitation mechanisms. Various electrochemical measurements have identified the S₂O₇ ^2? anion (dissolved SO₃) as the oxidant that is reduced in the hot corrosion process. Electrochemical polarization studies have elucidated the corrosion reactions and clarified the corrosion kinetics of alloys. Mechanistic models for Type I and Type II hot corrosion are discussed briefly.