Part XII – December 1969 – Papers - The Effect of Nickel on the Activity of Nitrogen in Fe-Ni-N Austenite

A capsule technique was successfully employed to investigate the effect of nickel on the activity of nitrogen in Fe-Ni-N austenite in the temperature range 600" to 1200°C. This technique consisted of equilibrating nitrogen among various Fe-Ni alloys within a sealed silica capsule. Nitrogen transfer among the specimens occurred by N, gas at 900°, lOOO? and 1200?C. Nitrogen gas pressures within the capsules were estimated to be as high as 22 atm. The activity coefficient of nitrogen, fN , in Fe-Ni-N austenite is adequately described by the linear interaction equation: log . wt pct Ni where the standard state is chosen such that fN = I as wt pct Napproaches zero in binary Fe-N. This relationship was determined over the temperature range 873" to 1473°K and for nickel contents of 0 to 35 wt pct. ALTHOUGH chemical thermodynamics of liquid iron alloys have been extensively studied, experimental data for the solid state are needed. These thermody-namic data will provide a basis for understanding phase transformations, precipitation reactions, metal-gas equilibria, and so forth. The interaction of sub-stitutional alloying elements with the interstitial elements is of particular interest. In this investigation the thermodynamic behavior of Fe-Ni-N austenite has been studied. The solubility of nitrogen gas in iron austenite is known to obey Sieverts&apos; law up to about 65 atm.1-6 In addition, the solubility of nitrogen in Fe-Ni austenite has been investigated5"8 using the classical method of equilibrating Fe-Ni alloys with nitrogen gas at 1 atm. A capsule technique similar to that used to study the activity of carbon in alloyed austeniteg&apos;&apos;&apos; was employed in the present work to determine the effect of nickel on the activity of nitrogen in Fe-Ni austenite over the temperature range 600" to 1200°C. EXPERIMENTAL PROCEDURE A series of Fe-Ni alloys up to 35 wt pct Ni was vacuum melted and cast into 1 by 3 by 6 in. ingots. Chemical analyses at the top and bottom of each ingot demonstrated that the ingots were homogeneous with respect to nickel content. The nickel contents are given in Table I. Additional chemical analyses showed that wt pct Si < 0.05, s < 0.01, C < 0.01, Al < 0.006, 0 < 0.004, Mn < 0.002, and P < 0.002. A 2 in. section of each ingot was cold rolled to 0.015 in. The material was then decarburized to a carbon content of less than 0.004 wt pct. A portion of the material of each nickel content was nitrided to various levels in a H2-NH3 gas atmosphere to provide a source of nitrogen during subsequent equilibration. The experimental technique consisted of equilibrating the series of Fe-Ni-N alloys in a partially evacuated sealed silica capsule at the temperature of interest. Both Vycor and quartz capsules were used. In general, the final equilibrium nitrogen content for each Fe-Ni alloy was approached from both higher and lower nitrogen levels. The criterion for establishing that equilibrium was attained was that the final nitrogen content for each Fe-Ni alloy was the same irrespective of the initial level. A schematic drawing of the sample configuration in a capsule is shown in Fig. 1. The samples were arranged so that there was a minimum of physical contact. The samples were also dusted with a fine, high purity alumina powder to help prevent sticking. Several different types of furnaces were used in this study. In each case, a thermocouple was placed immediately adjacent to the capsule during equilibration and the temperature was controlled to within *4?C of that reported. At each equilibration temperature, the following times were found to be more than sufficient to attain equilibrium: 600°C-250 hr, 900°C-150 hr, 1000°C-150 hr, and 1200°C-50 hr. After equilibration the capsules were quenched in water and the nitrogen contents of the specimens determined by a Strohlein analyzer. Analyses of samples after equilibration at 1000" and 1200°C showed no silicon pickup from the silica capsules. RESULTS AND DISCUSSION Transfer Mechanism. The mechanism by which nitrogen was transferred among specimens in an initially hydrogen flushed and partially evacuated capsule equilibrated at 1000°C was investigated. After equilibration the gas in the capsule was collected over water and an estimate of the pressure at temperature