Date of Original Version
This is the author’s version of a work that was accepted for publication. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version is available at http://dx.doi.org/10.1016/j.solidstatesciences.2014.12.016
Abstract or Description
Boron Carbide exhibits a broad composition range, implying a degree of intrinsic substitutional disorder. While the observed phase has rhombohedral symmetry (space group ), the enthalpy minimizing structure has lower, monoclinic, symmetry (space group Cm). The crystallographic primitive cell consists of a 12-atom icosahedron placed at the vertex of a rhombohedral lattice, together with a 3-atom chain along the 3-fold axis. In the limit of high carbon content, approaching 20% carbon, the icosahedra are usually of type B11 Cp, where the p indicates the carbon resides on a polar site, while the chains are of type C–B–C. We establish an atomic interaction model for this composition limit, fit to density functional theory total energies, that allows us to investigate the substitutional disorder using Monte Carlo simulations augmented by multiple histogram analysis. We find that the low temperature monoclinic Cm structure disorders through a pair of phase transitions, first via a 3-state Potts-like transition to space group R3m , then via an Ising-like transition to the experimentally observed symmetry. The R3m and Cm phases are electrically polarized, while the high temperature phase is nonpolar.
Solid State Sciences, 47, 21-26.