Oscillatory Kinetics in the Process of Reduction of Nanocrystalline Iron Nitride γ′-Fe4N

5 years ago

Oscillatory Kinetics in the Process of Reduction of Nanocrystalline Iron Nitride γ′-Fe4N

Rafał Pelka, Katarzyna Skulmowska, Walerian Arabczyk

The kinetics of the reduction of nanocrystalline γ′-iron nitride to α-iron in mixtures of nitrogen and hydrogen of different hydrogen concentration was studied. Kinetic measurements were carried out in a differential chemical reactor with a thermogravimetric system for measuring the weight of a sample and an analyzer of hydrogen at 400 °C and at atmospheric pressure. The occurrence of cyclic changes in the rate of chemical reaction in a solid phase has been observed. Such an oscillatory phenomenon was not observed so far in the reaction between gases and a solid with phase transition in a solid phase, which results in a solid products. The mechanism of the observed phenomenon is explained, taking into account processes occurring in the volume of the solid phase. The oscillatory rate changes of the described processes prove a nonmonotonic coverage degree of the surface with nitrogen, which is caused by a step change in the free enthalpy of segregation of nitrogen in the reduction of γ′-Fe₄N nitride. On the basis of model calculations the changes of free enthalpy of segregation during reduction of nitrides have been specified, and modification of the Fowler–Guggenheim equation has been proposed.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b04418

DOI: 10.1021/acs.jpcc.7b04418