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To investigate the morphology and the growth kinetics of nitrided layers of Fe-Cr alloys, nitriding experiments were performed for alloys with 4.3, 7.7, 14.0, and 21.5 at. pct Cr. The precipitation morphology of the nitrided samples was investigated with light optical microscopy and scanning electron microscopy (SEM). The elemental compositional variation was determined with electron probe microanalysis. To describe the evolution of the thickness of the nitrided layers, a numerical model was developed that has as important (fit) parameters: the surface nitrogen content, the solubility product of chromium and nitrogen dissolved in the ferrite matrix, and a parameter defining the composition of the precipitated chromium nitride. Fitting of the model to the experimental data demonstrated for the first time that mobile and immobile excess nitrogen is present in the nitrided layers and that the mobile excess nitrogen considerably influences the nitriding rate.

To accurately define important phase boundaries in the iron–nitrogen (temperature–composition) phase diagram as well as the (temperature–potential) Lehrer diagram, the solubility of nitrogen in ferrite was determined as a function of the nitriding potential (which defines the chemical potential of nitrogen) and the temperature. To this end, thin iron foils were homogeneously nitrided in flowing gas mixtures composed of ammonia and hydrogen. Phase identification was performed by means of X-ray diffraction analysis. Further, from the data obtained, the absorption function and the enthalpy for dissolution of nitrogen into ferrite and the enthalpy of the reaction occurring at the α/(α + γ′)-phase boundary were determined. The data obtained were corrected for the occurrence of a stationary state instead of a local equilibrium at the surface of the specimens. It followed that parts of the phase boundaries in the Lehrer diagram do not represent equilibrium states but rather stationary states.

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