Grain boundary complexion transitions in WO3- and CuO-doped TiO2 bicrystals

Abstract

Several grain boundary complexions (grain boundary interfacial phases) have been identified in TiO2 bicrystals by high-resolution transmission electron microscopy (TEM) and aberration-corrected scanning TEM (STEM). An intrinsic grain boundary with no apparent impurity segregation was observed in an undoped TiO2 bicrystal. In a WO3-doped TiO2 bicrystal, WO3 second-phase particles formed along the boundary, with a nominally clean, intrinsic-type grain boundary in between the particles. In a CuO-doped bicrystal, a remarkable series of three distinct grain boundary complexions with abrupt structural transitions was discovered coexisting at the grain boundary, and the existence of a fourth equilibrium complexion at the annealing temperature was implied. Thus, the WO3- and CuO-doped TiO2 bicrystals exhibit dramatically different solute partitioning behavior which can be understood in terms of the relative interphase boundary energies of these two systems. STEM–electron energy loss spectroscopy and energy-dispersive X-ray spectroscopy analysis of the nanoscale lens-shaped films of amorphous material in the CuO-doped TiO2 bicrystal demonstrated an excess of CuO, as expected, yet also revealed the unintentional presence of SiOx. The multiple grain boundary complexions in CuO-doped TiO2 offer an explanation for the CuO-enhanced grain growth and sintering of TiO2 that has been reported in the literature. Conversely, the intrinsic grain boundary complexion observed in WO3-doped TiO2 is consistent with previous work showing that WO3 has no effect on grain boundary mobility in TiO2. A phenomenological thermodynamic model is proposed to explain the physical origin of these observed grain boundary complexions and the abrupt, first-order complexion transitions that are believed to occur upon cooling of the CuO-doped TiO2 bicrystal.