Cementite (Fe3C) plays a major role in the tribological performance of rail and bearing steels. Nonetheless, the current understanding of its deformation behavior during wear is limited because it is conventionally embedded in a matrix. Here, we investigate the deformation and chemical evolution of bulk polycrystalline cementite during single-pass sliding at a contact pressure of 31 GPa and reciprocating multi-pass sliding at 3.3 GPa. The deformation behavior of cementite was studied by electron backscatter diffraction for slip trace analysis and transmission electron microscopy. Our results demonstrate activation of several deformation mechanisms below the contact surface: dislocation slip, shear band formation, fragmentation, grain boundary sliding, and grain rotation. During sliding wear, cementite ductility is enhanced due to the confined volume, shear/compression domination, and potentially frictional heating. The microstructural alterations during multi-pass wear increase the subsurface nanoindentation hardness by up to 2.7 GPa. In addition, we report Hägg carbide (Fe5C2) formation in the uppermost deformed regions after both sliding experiments. Based on the results of electron and X-ray diffraction, as well as atom probe tomography, we propose potential sources of excess carbon and mechanisms that promote the phase transformation
