Thermodynamics of Chemical Processes in the System of Nanocrystalline Iron–Ammonia–Hydrogen at 350 °C

Abstract

Nanocrystalline iron nitriding and the reduction of nanocrystalline iron nitrides in steady states at 350 °C are described using the chemical potential programmed reaction (CPPR), thermogravimetry (TG), 57Fe Mössbauer spectroscopy (MS), and X-ray diffraction (XRD) methods. It was determined that during the process of nitriding of nanocrystalline iron, larger nanocrystallites formed the γ’ phase and the smallest nanocrystallites (about 4%) were transformed into the α” phase. Both phases were in chemical equilibrium, with the gas phase at the temperature of 350 °C. Stable iron nitride α” was also formed in the ε iron nitride reduction process. Taking the α” phase in the system of nanocrystalline Fe-NH3-H2 into account, it was found that at certain nitriding potentials in the chemical equilibrium state, three solid phases in the nitriding process and four solid phases in the reduction process may coexist. It was also found that the nanocrystallites of ε iron nitride in their reduction process were transformed according to two mechanisms, depending on their size. Larger nanocrystallites of iron nitride ε were transformed into the α-iron phase through iron nitride γ’, and smaller nanocrystallites of ε nitride went through iron nitride α”. In the passivation process of nanocrystalline iron and/or nanocrystalline iron nitrides, amorphous phases of iron oxides and/or iron oxynitrides were formed on their surface.