Hydrogen reduction of cobalt ferrite

Abstract

The kinetics of reduction of cobalt ferrite by hydrogen as a function of reduction temperature and pressure have been measured by thermogravimetric analysis. A minimum in the rate as a function of temperature has been observed and its cause attributed to the formation of a cobalt-wiistite subscale at higher reduction temperatures. A mathematical model, based on one derived by Spitzer, Manning, and Philbrook,1 has been used to interpret the results in terms of the rate constants for the individual steps in the reaction. Optical microscopy has been used to characterize the morphology of the reduction product and, additionally, partially reduced single crystals of cobalt ferrite have been examined by transmission electron microscopy to characterize the microstructure of the reaction interface. A fine network of pores in the reduced scale was shown to allow the reducing and product gases to reach the immediate vicinity of the chemical reaction. The structure of the porosity and consequently the effective gaseous diffusion coefficient in the scale were both shown to be functions of the reduction temperature and pressure. The interface reaction was shown to follow Langmuir-Hinshelwood kinetics. A model was developed to explain such kinetics by incorporating a solid-state diffusion step. Such a step was considered necessary to explain the development of the observed microstructures. An ‘incubation time’ for the development of a continuous cobalt-wustite subscale at higher reduction temperatures was attributed to the different growth kinetics for the spinel-metal and spinel-wustite interfaces.