In Situ and Ex Situ X‑ray Diffraction and Small-Angle X‑ray Scattering Investigations of the Sol−Gel Synthesis of Fe₃N and Fe₃C

Iron nitride (Fe₃N) and iron carbide (Fe₃C) 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 Fe₃N/Fe₃C, we showed that the reaction proceeds as follows: Fe₃O₄ → FeO_x → Fe₃N → Fe₃C. 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 Fe₃N, and in an extensive laboratory study, we were indeed unable to isolate phase-pure Fe₃N. However, we made the surprising discovery that Rietveld-pure Fe₃C 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 Fe₃C nanoparticles.