Cu–Si phase equilibria have been investigated at compositions greater than 72 at.% Cu by X-ray diffraction, optical and electronic microscopy, electron probe microanalysis and differential thermal analysis.The general aspects of the phase equilibria already reported in literature have been substantially confirmed, but selected composition ranges and the nature of a few invariant equilibria have been modified. In particular stability ranges of the β, δ and η phases have been slightly modified as well as temperature and nature of the invariant equilibria related to the γ ⇄ δ transformation.Stability of the ɛ-(Cu15Si4) phase has been especially investigated concluding that it is thermodynamically stable but kinetically inhibited by nucleation difficulties which become especially effective when samples are synthesized in very high purity conditions.Crystal structure and composition ranges of the high temperature β and δ phases, despite difficulties by the non-quenchability of these phases, have been investigated by different methods including high temperature XRD.

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