RI 9491 - Annealing Study of Stainless Steel To Conserve Critical Metals

The U.S. Bureau of Mines investigated the oxidation of American Iron and Steel Institute (AISI) Type 304 stainless steel (SS) during annealing in simulated combustion products from several air-CH4 fuel ratios. Atmospheres representing air-CH4 ratios of 14:1 and 18:1 contained free 02, while atmospheres representing 10:1 air-CH, ratio did not. A Cr203 layer formed on SS samples annealed in atmospheres containing free 0, while a Cr-Fe spinel layer formed in atmospheres with no free 02. The Cr203 layer was adherent and presented a protective barrier to metal diffusion, effectively limiting oxidation of the metal substrate. The Cr-Fe spinel was not protective and allowed the diffusion of Fe through the spinel to the gas-oxide interface where it was oxidized to magnetite, which spalled from the surface. This resulted in thick scale layers on samples annealed in atmospheres containing no free 02, as compared to layers formed on samples annealed in atmospheres containing free 02. These results confirmed and explained industrial operators' observations that thick, smoky (fine spalled magnetite) scales form on SS annealed in low free-02 atmospheres, while thin protective oxide layers form on sheets in atmospheres containing free 02.