Formation of Fe3N, Fe4N and Fe16N2 on the surface of iron

In order to clarify the phenomenon of nitride formation on the surface of iron, highly polished specimens of well refined and coarsened iron grains have nitrided in flowing H2 + NH3 gas. The morphology and the conditions for formation of Fe₃N are clarified; it forms only on the surface of {lll}_α or near {lll}_α grains and grows in {112}_α directions during nitriding treatment at temperatures between 450 and 550°C. Fe₁₆N₂ and Fe₄N are also formed preferentially on the surfaces of {00l}_α and {210}_α grains, respectively. It is suggested that these iron surfaces are those satisfying the coherency relationships between nitrides and iron matrices. The morphologies and the formation temperature regions of Fe₁₆N₂ and Fe₄N on the surface of iron are quite different to those observed in iron. In particular, Fe₁₆N₂, which has been generally accepted as metastable in bulk iron below 200°C, can exist even at temperatures from 450 to 500°C when it is formed on the surface of iron.