Dissolution behavior of 304 stainless steel in HNO3/HF mixtures

The dissolution behavior of type 304 stainless steel was studied in typical pickling environments in an effort to reduce the unnecessary loss of the critical metals nickel and chromium during the pickling process. Dissolution rates were determined for a 90-minute exposure to HNO₃/HF solutions ranging from 0.8 M to 3.5 M HNO₃ and 0.5 M to 2.6 M HF at 30°, 50°, 70°, and 90 °C and containing 0 to 0.21 M dissolved Fe, Cr, or Ni. Dissolution rates increased as a function of increasing HNO₃ concentration from 0.4 M to 1.5 M HNO₃, decreased at higher HNO₃ concentrations, and increased with increasing HF concentration. Experiments to determine the effect of temperature on the dissolution reaction gave a lower activation energy for solutions with higher HNO₃ concentrations. The dissolved Fe and Cr decreased the dissolution rate of 304 stainless steel, while dissolved Ni had essentially no effect. The Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) studies of films resulting from exposure to several HNO₃/HF solutions indicated that the fluoride did not penetrate the thin nonprotective films but remained on the outer surface of the film. The scanning Auger microscopy (SAM) studies indicated that the fluoride was uniformly distributed over the surface. Both the dissolution and surface studies are consistent with a dissolution process which is controlled by reactions occurring either in solution or at the film-solution interface.