PART IV - Papers - A Model for Concentrated Interstitial Solid Solutions; Its Application to Solutions of Carbon in Gamma Iron

A simple rnodel for interstitial solid solutions has been devised in which each solute atom interacts with the solzlent lattice in such a way as to exclude an integral number of nearest-neighbor sites from being occupied by solute atoms. The vemaining interstitial sites ave not affected. In calculating the entropy of such a solution the increase in the number of interstitial sites available to solute atoms due to the ozlerlap of blocked sites is taken into account. The ther-modynamic functions and the solute activity fov the solution rnodel are calculated. It is shown that considevation of the overlap sues vise to a correction term of the order 8' ( where 0 is the ratio of solute to solvent atoms) in the thevmodynamic functions of the solution and the solute activity. The theo,uetical equation for the solute activity was used to analyze the available data for the activity of carbon in austenite at three different temperatures. The use of a computer enabled many comparisons to be made between the experimental activity data and those predicted by both the complex blocking model and the simple, widely used blocking model in which the ozierlapping of blocked sites is not taken into consideration. Even though at the highest concentvations oj carbon the value of 0 is small it is shown that the best fit to the experimental data is found with the complex blocking model. RECENTLY it has been shown by analysis of gas-solid equilibriums that many interstitial solid solutions can be described by the quasi-regular solution model in which the partial energy of solution E, is independent of composition and, apart from a composition-independent term due to nonconfigurational factors, the partial entropy is that of an ideal solution. Dilute solutions of nitrogen in both bcc and fcc iron,' dilute solutions of oxygen and silver,' carbon in a Fe,' and dilute solutions of carbon in ? Fe2 are all quasi-regular. In addition many hydrogen-metal solutions, both dilute and concentrated (with the notable exceptions of the H-Ni and H-Pd systems), can be described by this model.3 However, it has been shown that, at various temperatures, solutions of carbon in ? Fe begin to depart strongly from quasi-regular behavior at low concentrations. A plot of the activity of carbon in ? Fe relative to pure graphite vs atom fraction of carbon (Cc) calculated from Smith's data4 begins to depart from the (nonlinear) plot for a quasi-regular solution at about Cc = 0.02. Several statistical models have been proposed to account for the thermodynamic behavior of carbon in y Fe. Darken and smith4 set up a model in which a carbon atom in its octahedral site in the fcc lattice has either one or no neighboring carbon atoms in the twelve nearest-neighbor octahedral sites. It is assumed that the number of carbon atoms having more than one nearest neighbor is negligibly small and that a solute atom does not interact with another solute atom located at a greater distance than the first shell of interstitial sites. Thus this model contains two characteristic interaction energies. Darken and Smith showed that this model gives reasonable agreement with the measured variation of carbon activity ac with composition. It is noteworthy that Darken and Smith concluded from their analysis of the activity data using this model that there was a repulsive force between carbon atoms in austenite which reduces the concentration of C-C pairs below that corresponding to random mixing. Recently Aaronson, Domian, and pound5 have considered in detail the statistical model developed by Lachere and by Fowler and Guggenheim7 and have shown that it is compatible with the activity data for carbon in austenite. In Darken's model the energy of solution of carbon in austenite is dependent on temperature and concentration; the departure from Henry's law arises from the concentration dependence of the energy of solution. In Aaronson, Domian, and Pound's discussion of the Lacher, Fowler, Guggenheim model the interaction energy wy between adjacent carbon atoms in austenite is strongly temperature-dependent. Aaronson et al . suggested that this temperature dependence of wy and hence the energy of solution of carbon could be explained either by the formation of clusters of carbon atoms (despite the repulsive nature of wy) or by the dual occupancy of the octahedral and tetrahedral sites by the carbon atoms. However, a temperature-dependent heat of solution