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Sigma-Phase Embrittlement
By Daniel H. Herring February 29, 2012 Enlarged Image Enlarged Image Many stainless steels and other iron-chromium alloys are susceptible to a grain boundary phenomenon known as sigma-phase embrittlement. This type of embrittlement has been shown to cause severe loss of ductility, toughness, and corrosion resistance resulting in cracking (Fig. 1) and failure of components, especially those subjected to impact loads or excessive stress. As heat treaters we need to know more about what sigma-phase embrittlement is and how to avoid its occurrence. Lets learn more.
Prolonged exposure in the temperature range of 565-925C (1050-1700F) results in chromium depletion from the grain boundaries, making them susceptible to intergranular corrosion. The most rapid sigma-phase formation occurs in the range of 700-900C (1290-1650F). Alloy elements such as molybdenum, titanium and silicon promote the formation of sigma phase, while nitrogen and carbon reduce its tendency to form. Sigma phase is an intermetallic compound consisting of chromium and iron, which is hard, brittle and non-magnetic. Pure sigma forms between 42% and 50% chromium and is one of the equilibrium phases in the iron-chromium phase diagram (Fig. 2). A duplex structure (sigma and alpha phases) has been found to form in alloys with as little as 20% chromium and as much as 70% chromium when exposed to the critical temperature range noted above. At chromium contents of less than 20%, sigma phase is difficult to form, but the presence of molybdenum, silicon, manganese or nickel have a tendency to shift the lower limit down. Molybdenum reportedly promotes sigma-phase formation much more effectively than chromium, particularly at temperatures around 900C (1650C). This is why, in the HH cast stainless example shown, the molybdenum content of the alloy is deliberately kept around 0.5%. Austenite-forming elements such as nickel or nitrogen can also accelerate the nucleation and growth of the sigma phase, although these elements may reduce the total amount formed because of the smaller volume fraction of ferrite. Sigma typically nucleates in the austenite-ferrite grain boundaries and grows into the adjacent ferrite. Additional austenite often forms in the areas of chromium depletion adjacent to the sigma phase. Although the formation of sigma phase is sluggish, cold working enhances the precipitation rate considerably, and sigma phase has even been found in the air-cooled, as-cast structures in very high chromium content alloys. Sigma phase usually appears as a continuous network in the microstructure. Since sigma has a significantly lower corrosion resistance compared to the ferrite matrix, its presence can be detected by etching in a metallographic examination (Fig. 3). The temperature range of rapid sigma formation coincides with the normal temperatures used for annealing ferritic stainless steels. Consequently, highly alloyed ferritic stainless steels must be annealed in the 1050C (1925F) range and rapidly cooled through the critical range to avoid sigma-phase embrittlement. Any sigma phase already formed can be dissolved again by a solution-annealing process performed above 800-850C (1470-1560F) for relatively short
Fig. 1. Section of a cast HH (25% Cr, 12% Ni) stainless steel furnace load-lifting hook that failed due to sigma-phase embrittlement. (Photograph courtesy of George F. Vander Voort, Vander Voort Consulting LLC)
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Sigma-Phase Embrittlement
http://www.industrialheating.com/articles/print/90371-sigma-phase-emb...
times approximately an hour (once the entire part has reached temperature) followed by air cooling.
Fig. 3. Sigma phase (dark areas) precipitated from excessive ferrite in the cast HH stainless steel furnace hook, causing it to fracture extensively. (Photograph courtesy of George F. Vander Voort, Vander Voort Consulting LLC)
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Sigma-Phase Embrittlement
http://www.industrialheating.com/articles/print/90371-sigma-phase-emb...
Summing Up
The presence of sigma phase in stainless steels and iron-chromium alloys should be cause for concern among heat treaters, but awareness of what can trigger this form of embrittlement and what can be done to negate its effects are worth our time and effort. IH
Dan Herring is president of THE HERRING GROUP Inc., which specializes in consulting services (heat treatment and metallurgy) and technical services (industrial education/training and process/equipment assistance. He is also a research associate professor at the Illinois Institute of Technology/Thermal Processing Technology Center.
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