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The synthesis, phase relations, and crystal structures of two truly ternary, partially ordered Laves phases occurring in the V—Co—Si system are reported. The phases termed L1 V(Co 1–x Si x ) 2  are found in two distinct phase fields next to TiMnSi-type VCoSi. This so-called E-phase emerges in the centre of the miscibility gap which separates the Co- and Si-rich Laves phase fields. Both fields accommodate several structurally distinct L-phases. The L1-phases V(Co 1–x Si x ) 2  ( x  = 0.43 and 0.56) crystallise in √3 a  × √3 a  superstructures of the hexagonal MgZn 2  structure type. A rigorous symmetry-based analysis reveals that, at the given compositions, this type of superstructure affords sufficient structural degrees of freedom for ordering of Co and Si atoms on 4 different sites in a manner that enables tuning of hetero-atomic Co—Si interactions to an optimum.

Atomic ordering in the Laves phases L1 V(Co 1–x Si x ) 2 ( x = 0.43 and 0.56)