Hydrogen and water vapour effects on oxygen solubility and diffusivity in high temperature Fe-Ni alloys

摘要

It is a worldwide priority to reduce emissions of greenhouse gases such as CO2. One solution for reducing these emissions is to improve the efficiency of energy production units by increasing their operating temperature. However, in order to increase operating temperature, new austenitic materials based on the Fe-Ni-Cr system have to be designed. In addition, these materials need to exhibit good protection against high temperature oxidation, which is achieved by the formation of a slow growing chromium oxide or alumina scale on the metal. However, to predict the formation of a protective scale, knowledge of the oxygen permeability, the product of oxygen solubility and diffusivity, in the base alloy is required. The objective of this study is to measure the permeability, solubility and diffusivity of oxygen in Fe- Ni alloys at temperatures above 1,000°C. In order to obtain the best results, the formation of an external oxide layer during the experiment has to be avoided. To achieve this, the oxygen partial pressure was fixed at the Fe/FeO equilibrium pressure in all experiments. In addition, two types of atmospheres were used: one dry and one wet, in order to investigate the effect of water vapour on oxygen permeability, solubility and diffusivity. The dry atmosphere was achieved using the Rhines Pack technique. The samples were oxidised in vacuum-sealed quartz capsules, which contained a mixture of powdered iron and wüstite. The humid atmosphere was obtained by using H2/H2O gas mixtures with the appropriate water vapour to hydrogen ratio to fix oxygen partial pressure at the Fe/FeO equilibrium. The maximum oxygen solubility was found in pure iron, and decreased continuously with nickel additions to the alloy. The dependence of solubility on alloy composition is non-ideal, and cannot be predicted from simple models. Moreover, the presence of water vapour in the atmosphere seems to increase the solubility by a factor of 2 in alloys with nickel content lower than 80 at.% at temperatures near 1,000°C. However, at 1,150°C the solubility of the oxygen is independent of the environment. The oxygen permeability was determined by measuring the internal oxidation kinetics of Fe-Ni-Cr alloy. These kinetics were evaluated by measuring the internal oxidation zone depth by optical microscopy, or by continuous and discontinuous thermogravimetry. Results showed that the oxygen permeability exhibits the same variation with alloy composition as the oxygen solubility, independent of the atmosphere. In particular, no significant effect of water vapour on oxygen permeability values was observed. In the present study, the oxygen diffusion coefficient was also determined using permeability, in addition to the independent measurement of the oxygen solubility carried out in the present study. For temperature above 1,000°C, the variation of oxygen diffusion coefficient with the alloy composition is similar in all environments tested, and a maximum is observed for alloys with a nickel content of 40 at.%. However, for a given nickel content up to 60 at.%, the presence of water vapour in the atmosphere decreases the value of the oxygen diffusion coefficient by a factor of 2-3 at 1,000°C. In addition, this difference between diffusion coefficients measured in a dry and wet atmosphere increases as the temperature decreases. Overall, it was found that the water vapour has no effect on the way in which oxygen permeability, solubility and diffusivity vary with the alloy composition. However, the presence of water vapour in the environment appears to increase the oxygen solubility and decrease the oxygen diffusivity in iron-rich alloys, the effect being more significant at low temperatures. These results suggest further research into interactions between O, H and metal vacancies, particularly for temperature around 1,000°C and below, as the latter defect is thought to change the diffusion and solubility properties of interstitial species.