In this paper, a method of using the second phase to control the grain growth in Fe–Al–Cr alloys was proposed, in order to obtain better mechanical properties. In Fe–Al–Cr alloys, austenitic transformation occurs by adding austenitizing elements, leading to the formation of the second phase and segregation at the grain boundaries, which hinders grain growth. FeCr(σ) phase was obtained in the Fe–Al–Cr alloys, which had grains of several microns and was coherent and coplanar with the matrix (Fe2
AlCr). The nucleation of σ phase in Fe–Al–Cr alloy was controlled by the ratio of nickel to chromium. When the Ni/Cr (eq) ratio of alloys was more than 0.19, σ phase could nucleate in Fe–Al–Cr alloy. The relationship between austenitizing and nucleation of FeCr(σ) phase was given by thermodynamic calculation.
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