Corrosion of 310 stainless steel in H₂-H₂O-H₂S gas mixtures: studies at constant temperature and fixed oxygen potential

Abstract

Corrosion of SAE 310 stainless steel in H₂-H₂O-H₂S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10^-13 Nm^-2 and sulfur potentials ranging from 0.19 × 10^-2 Nm^-2 to 33 × 10^-2 Nm^-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (P_S2 ≥ 2.7 × 10^-2 Nm^-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials (P_S2 ≤ 0.19 × 10^-2 Nm^-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.