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Crevice corrosion behaviour of nickel based alloys in neutral chloride solutions Mulford, Stephen John

Abstract

Crevice corrosion experiments have been conducted on Inconel 600 and Inconel 625 exposed to two principle test solutions of 1 M NaCl and 1 M NaCl + 0.01 M Na₂S₂0₃ (Sodium Thiosulphate) at three temperatures, 22°C, 55 °C and 80°C. The crevice corrosion tests were performed in a corrosion cell which was constructed from PTFE (Polytetrafluoroethylene, Teflon) and Pyrex glass. Features of the cell included the utilization of an artificial Teflon-metal crevice and provisions to monitor crevice corrosion current, active crevice corrosion potential and active crevice pH. Additional experiments included potentiodynamic anodic polarization tests on pure Ni, Alloy 600, and Alloy 625 in bulk solution environments and in simulated crevice solutions. Crevice corrosion morphology and compositional analysis of the corrosion products was studied using a scanning electron microscope equipped with an X-ray energy dispersive spectroscopy (EDS) system. Results show that crevice corrosion rates increase with increasing temperature for Alloy 600 in both principle test solutions. X-ray EDS analysis indicated that an insoluble nickel sulphide corrosion product formed on Alloy 600 in a solution of 1 M NaCl + 0.01 M Na₂S₂0₃. For the Alloy 600, in a solution of 1 M NaCl + 0.01 M Na₂S₂0₃, initiation times were significantly reduced and crevice corrosion propagation rates enhanced, as compared to Alloy 600 in 1 M NaCl. The decrease in initiation times has been attributed to the destabilizing nature of the S₂O₃⁻² species on the passive oxide film. Enhanced propagation rates have been attributed to the presence of H₂S in the crevice solution and the formation of an adsorbed species Ni(H₂S)ads which enhances the anodic dissolution reaction. The H₂S in the active crevice solution originated from the thermodynamically favoured electrochemical reduction of the S₂0₃⁻² species in the active crevice solution. Experiments on Alloy 625, which is alloyed with molybdenum, (Mo), show that it was virtually immune to crevice corrosion as compared to Alloy 600 which is not alloyed with Mo. The resistance of Alloy 625 to crevice corrosion initiation has been attributed to the stabilizing nature of MoO₂ in the passive oxide film. For an actively corroding system, the formation of the molybdate species MoO₄⁻² may act as an anodic inhibitor and effectively enhance the repassivation of the passive film.

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