Change in pH and Chloride Concentration inside Crevice of Stainless Steels

Abstract

Stainless steels sometimes suffer from crevice corrosion in chloride environments. The pH value and Cl- concentration are important factors in the initiation and growth of crevice corrosion. Nishimoto et.al.[1] fabricated a glass plate with a sol-gel SiO2 sensing layer, which contains a pH indicator and a Cl- sensitive florescent dye, and the pH and Cl- distributions in the crevice solution for stainless steel were visualized simultaneously. The specimens used in this study were cut from a Type 430 stainless steel sheet (0.035%C, 0.20%Si, 0.38%Mn, 0.019%P, 0.005%S, 0.19%Ni, 15.9%Cr in mass%). The specimens were heat-treated at 1123 K for 600 s and water-cooled. The size of the specimen was 4 mm×3 mm×20 mm. The specimen surfaces were polished by a 1 μm diamond past. To fabricate the sensing plate for the simulations measurements of pH and Cl- concentration, Terbium-dipicolinic acid complex (Tb-DPA) and quinine sulfate as the fluorescent dyes were chosen. Tb-DPA was used as the sensing dye for the pH measurements, and quinine sulfate was used to measure the Cl- concentration. Tb-DPA was formed by mixing Tb­­2(SO4)3 and dipicolinic acid. A sol-gel method was used to make the sensing layer, which contained two fluorescent dyes, onto one side of a quartz glass plate. Figure 1 shows the illustration of a crevice corrosion test cell. In crevice corrosion tests, the crevice was formed between the sensing plate and specimen. Potentiostatic polarization was performed at 0.15 V (vs. Ag/AgCl, 3.33 M KCl) in 10 mM NaCl (pH 3.0). During crevice corrosion tests, the surface images of the specimen were taken under UV irradiation, and pH and Cl- values were calculated from the fluorescence images. The details were described in the literature. [1] Figure 2 shows the surface appearance and the images of pH and Cl- distributions at the initiation point of the crevice corrosion at 1500 s. The pH and Cl- were calculated by the brightness of fluorescence images. A pit was initiated inside the crevice. Before the initiation of crevice corrosion, it was elucidated that the pH at the initiation point of gradually decreased with time, and that the Cl- concentration increased with time. On the basis of time variations of the pH and Cl- concentration, the initiation and growth mechanims of the crevice corrosion of stainales steels were determiend. References; Nishimoto, J. Ogawa, I. Muto, Y. Sugawara, N. Hara: Corros. Sci., 106, 298-302(2016) Figure 1