Journal of the Southern African Institute of Mining and Metallurgy
On-line version ISSN 2411-9717
Alloys used at high temperature must resist both creep and corrosion. Design for corrosion resistance is based on the formation of a slow-growing, protective oxide scale by selective oxidation of an appropriate alloy component, usually chromium or aluminium. A successful scale will exclude other corrodents, notably carbon, which can otherwise cause extremely rapid corrosion at high temperatures. Selective oxidation of an alloy component necessarily lowers the concentration of that metal in the alloy subsurface region. Under thermal cycling conditions, mechanical damage to the scale leads to renewed oxide growth and accelerated alloy depletion. Eventually, a point is reached where diffusion of a corrodent into the alloy becomes competitive with the outward diffusion of alloy metal to repair the protective scale. Two examples of alloy failure by carbon attack are considered. In the steam cracking (pyrolysis) process, centrifugally cast tubes of heat-resisting alloy are exposed to a gas stream of hydrocarbon and steam, at a carbon activity of unity. Formation and repair of the surface chromia scale causes alloy depletion, Kirkendall void formation, and subsequent internal precipitation of chromium-rich carbides. Their formation makes chromia scale formation much more difficult, and generates internal stress. Eventually, the tubes fail by creep rupture. In other processes (e.g. steam reforming, heat treatment), synthesis gases are supersaturated with carbon at intermediate temperatures. Once the alloy's protective scale is breached, carbon attacks the depleted substrate. In the case of ferritic alloys, it forms a surface scale of Fe3C. As this scale thickens, the supersaturated carbon precipitates as graphite within its outer regions. The resulting volume expansion causes disintegration of the cementite in a process known as metal dusting. In the case of austenitic alloys, no metal carbide is formed. Instead, carbon dissolves in the depleted metal to diffuse inward and precipitate as graphite within the metal matrix. Again, volume expansion causes disintegration of the alloy, and metal dusting results. Dusting occurs at an extraordinarily rapid rate, and leads to failure by section loss or even penetration.
Keywords : high-temperature corrosion; oxidation; carburization; metal dusting.