Stress corrosion cracking of duplex stainless steels in caustic solutions

Duplex stainless steels (DSS) with roughly equal amount of austenite and ferrite phases are being used in industries such as petrochemical, nuclear, pulp and paper mills, de-salination plants, marine environments, and others. However, many DSS grades have been reported to undergo corrosion and stress corrosion cracking in some aggressive environments such as chlorides and sulfide-containing caustic solutions. Although stress corrosion cracking of duplex stainless steels in chloride solution has been investigated and well documented in the literature but the SCC mechanisms for DSS in caustic solutions were not known. Microstructural changes during fabrication processes affect the overall SCC susceptibility of these steels in caustic solutions. Other environmental factors, like pH of the solution, temperature, and resulting electrochemical potential also influence the SCC susceptibility of duplex stainless steels.;In this study, the role of material and environmental parameters on corrosion and stress corrosion cracking of duplex stainless steels in caustic solutions were investigated. Changes in the DSS microstructure by different annealing and aging treatments were characterized in terms of changes in the ratio of austenite and ferrite phases, phase morphology and intermetallic precipitation using optical micrography, SEM, EDS, XRD, nano-indentation and microhardness methods. These samples were then tested for general and localized corrosion susceptibility and SCC to understand the underlying mechanisms of crack initiation and propagation in DSS in the above-mentioned environments.;Results showed that the austenite phase in the DSS is more susceptible to crack initiation and propagation in caustic solutions, which is different from that in the low pH chloride environment where the ferrite phase is the more susceptible phase. This study also showed that microstructural changes in duplex stainless steels due to different heat treatments could affect their SCC susceptibility. Annealed and water quenched specimens were found to be immune to SCC in caustic environment. Aging treatment at 800°C gave rise to sigma and chi precipitates in the DSS. However, these sigma and chi precipitates, known to initiate cracking in DSS in chloride environment did not cause any cracking of DSS in caustic solutions. Aging of DSS at 475°C had resulted in '475°C embrittlement' and caused cracks to initiate in the ferrite phase. This was in contrast to the cracks initiating in the austenite phase in the as-received DSS. Alloy composition and microstructure of DSS as well as solution composition (dissolved ionic species) was also found to affect the electrochemical behavior and passivation of DSS which in turn plays a major role in stress corrosion crack initiation and propagation. Corrosion rates and SCC susceptibility of DSS was found to increase with addition of sulfide to caustic solutions. Corrosion films on DSS, characterized using XRD and X-ray photoelectron spectroscopy, indicated that the metal sulfide compounds were formed along with oxides at the metal surface in the presence of sulfide containing caustic environments. These metal sulfide containing passive films are unstable and hence breaks down under mechanical straining, leading to SCC initiations. The overall results from this study helped in understanding the mechanism of SCC in caustic solutions. Favorable slip systems in the austenite phase of DSS favors slip-induced local film damage thereby initiating a stress corrosion crack. Repeated film repassivation and breaking, followed by crack tip dissolution results in crack propagation in the austenite phase of DSS alloys. Result from this study will have a significant impact in terms of identifying the alloy compositions, fabrication processes, microstructures, and environmental conditions that may be avoided to mitigate corrosion and stress corrosion cracking of DSS in caustic solutions.