Corrosion of Stainless Steels S31603, S31655, and S32101 in Sulfuric Acid Solutions: Effects of Concentration, Chlorides, and Temperature

This study investigates the corrosion behavior of three stainless steel grades at two H₂SO₄ concentrations, namely 1 wt% and 10 wt%, with varying NaCl concentrations in the range from 500 mg/L to 10,000 mg/L. Dissociation of sulfuric acid yields the hydrogen (H⁺) and sulfate (SO²₄^-) ions, the former of which lowers the pH value of a solution while the latter increases the concentration of sulfate ions that act as a corrosion inhibitor. The equilibrium chemistry of the solutions was defined at the test temperatures of 22°C, 50°C, 90°C, and 130°C, and correlated with the observations on the electrochemical and microstructural examination of the materials. The results showed clear differences in the main corrosion form between the two H₂SO₄ concentrations. In 1 wt% H₂SO₄, pitting was the major form of corrosion attack in the presence of chlorides, whereas uniform corrosion dominated in 10 wt% H₂SO₄. The pitting corrosion tendency for the three stainless steel grades under various test conditions was consistent, but there were differences in their resistance to uniform corrosion. The chloride-to-sulfate activity ratio, a(Cl^-)=a(SO²₄^-), was found to be the key parameter in defining the occurrence of pitting corrosion for all three alloys. In H₂SO₄-NaCl systems, no pitting occurred at the activity ratio a(Cl^-)=a(SO²₄^-) below 10, with higher values inducing pitting attack, particularly in 1 wt% H₂SO₄. The described novel results are presented and discussed in this paper.