Published online by Cambridge University Press: 25 February 2011
Large grain polycrystalline boron carbides have a high-temperature thermal conductivity which changes from being characteristic of a crystal to being glass-like as the carbon content is reduced from its maximal value. We relate this phenomenon, to compositional changes within the three-atom intericosahedral chains. With a reduction of the carbon concentration from its maximal concentration (20 %), a carbon atom within some of the three-atom (CBC) intericosahedral chains is replaced by a boron atom, thereby producing CBB chains. We estimate that the CBB chains are significantly softer than the CBC chains. Thus, with this reduction of carbon content the intericosahedral chains are inhomogeneously softened. This suppresses the coherent transport of heat through the chains. The remaining thermal transport occurs incoherently through vibrationally inequivalent structural units, i.e. “phonon hopping.”