Gaseous nitriding of steel and iron can significantly improve their properties, for example corrosion resistance, fatigue endurance and tribological properties. In order to obtain a better understanding of the early stages of formation of the initial cubic primitive γ′-Fe4N, the mechanism and crystallography of the α–γ′ phase transformation was investigated under simplified conditions. Single-crystal α-Fe whiskers were nitrided at 823 K and a nitriding potential of 0.7 atm−1/2 for 20 min. The resulting microstructure and phases, as well as the crystallographic orientation of crystallites belonging to a particular phase, were characterized by scanning electron microscopy coupled with electron backscatter diffraction. The habit planes were investigated by single- and two-surface trace analysis. The α-Fe whiskers partly transform into γ′-Fe4N, where γ′ grows mainly in a plate-like morphology. An orientation relationship close to the rational Pitsch orientation relationship and {0.078 0.432
0.898}α and {0.391 0.367
0.844}γ′ as habit planes were predicted by the phenomenological theory of martensite crystallography (PTMC), adopting a {101}α〈101〉α shear system for lattice invariant strain, which corresponds to a {1
1
1}γ′〈1
12〉γ′ shear system in γ′. The encountered orientation relationship and the habit planes exhibit excellent agreement with predictions from the PTMC, although the transformation definitely requires diffusion. The γ′ plates mainly exhibit one single internally untwinned variant. The formation of additional variants due to strain accommodation, as well as the formation of a complex microstructure, was suppressed to a considerable extent by the fewer mechanical constraints imposed on the transforming regions within the iron whiskers as compared to the situation at the surface of bulk samples.
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