Study of reaction sequences during MSR synthesis of TiC by controlled ball milling of titanium and graphite

During reactive ball milling of Ti and C, mechanically induced self-propagating reaction (MSR) synthesis of TiC is reported to occur via a process including initial formation of small amounts of TiC prior to exothermic ignition, followed by MSR and the formation of stiochiometric TiC (Dorofeev et al., 2011; Oghenevweta et al., 2016 [1, 2]). However, both the chemical evolution and mechanisms of reaction and growth of TiC both prior to, during and after ignition are not fully understood. This research focuses on fundamental understanding of the reaction sequences during MSR synthesis of TiC from elemental Ti and C (graphite). Magnetically controlled ball milling of stoichiometric (1:1) powder mixtures of titanium (Ti) and graphite (C) was performed under He gas with the exothermic ignition point by determined via in-situ temperature measurement. X-ray diffraction, Scanning Transmission Electron Microscopy (STEM) with electron energy loss spectroscopy (EELS), Raman Spectroscopy and X-ray Photoelectron Spectroscopy (XPS) were employed to interpret the reaction sequences. The reaction sequence involved the following: During milling prior to ignition, severely deformed Ti, spheriodised graphite and amorphous carbon forms, and minor amounts of off-stiochiometric nano-TiC1−x crystals. In addition to the formation of TiC1−x, XPS revealed the formation of oxide skins coating the surface regions of the milled powders. There is also an evolution towards stiochiometric TiC with increasing milling time. Immediately after ignition, a reacted product comprising a mixture of multi-layer stacks of thin TiC plates form, in addition to a matrix comprising large TiC particles which have been liquid phase sintered under the high local heat of reaction by thin layers of unreacted Ti. MSR occurs via a dual mechanism involving rapid growth of existing TiC, plus nucleation and growth of new TiC. High spatially resolved EELS combined with STEM revealed additional information about the inhomogeneous chemical environment of the milled powders