Part II – February 1968 - Papers - On the Anomalous Behavior of Hydrogen in Iron at Lower Temperatures

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each