Mechanism of Transformation of Ferrocene into Carbon-Encapsulated Iron Carbide Nanoparticles at High Pressures and Temperatures.

Abstract

A mechanism was established for the formation of nanosized iron carbide particles encapsulated in carbon shells via the processes of ferrocene thermal conversions at high pressures. At a pressure of 8.0 GPa, products of ferrocene decomposition were studied as a function of temperature by X-ray diffraction, Raman and Mössbauer spectroscopy, scanning and transmission electron microscopy. It was shown that the mechanism of formation of the carbon-encapsulated iron carbide nanoparticles at high pressures and temperatures differs qualitatively from the known mechanism of their formation in the gas-phase processes of laser pyrolysis or photolysis of ferrocene. At high pressures and temperatures, the formation of iron carbide nanoparticles occurs not due to the primary growth of pure iron particles and the subsequent dissolution of carbon in iron. Nanoparticles are formed due to the direct fusion of iron-carbon clusters, which are formed at intermediate stages of ferrocene thermal destruction. Then, obtained amorphous iron carbides Fe1- xC x with a high carbon content start to crystallize. Two crystalline carbon-encapsulated forms of iron carbide (Fe7C3 and Fe3C) are the main products of crystallization of the amorphous Fe1- xC x depending on the temperature of the ferrocene treatment.