In Situ and Ex Situ X-ray Diffraction and Small-Angle X-ray Scattering Investigations of the Sol-Gel Synthesis of Fe 3 N and Fe 3 C.

Iron nitride (Fe 3 N) and iron carbide (Fe 3 C) nanoparticles can be prepared via sol-gel synthesis. While sol-gel methods are simple, it can be difficult to control the crystalline composition, i.e. , to achieve a Rietveld-pure product. In a previous in situ synchrotron study of the sol-gel synthesis of Fe 3 N/Fe 3 C, we showed that the reaction proceeds as follows: Fe 3 O 4 → FeO x → Fe 3 N → Fe 3 C. There was considerable overlap between the different phases, but we were unable to ascertain whether this was due to the experimental setup (side-on heating of a quartz capillary which could lead to thermal gradients) or whether individual particle reactions proceed at different rates. In this paper, we use in situ wide- and small-angle X-ray scattering (wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS)) to demonstrate that the overlapping phases are indeed due to variable reaction rates. While the initial oxide nanoparticles have a small range of diameters, the size range expands considerably and very rapidly during the oxide-nitride transition. This has implications for the isolation of Rietveld-pure Fe 3 N, and in an extensive laboratory study, we were indeed unable to isolate phase-pure Fe 3 N. However, we made the surprising discovery that Rietveld-pure Fe 3 C nanoparticles can be produced at 500 °C with a sufficient furnace dwell time. This is considerably lower than the previous reports of the sol-gel synthesis of Fe 3 C nanoparticles.