Institute of Metals Division - Diffusion of Nitrogen in Iron

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global