Abstract
A new previously unknown effect of a reversible transition from a single-phase system to a heterophase system containing a non-autonomous phase was observed during thermal and chemical deformations of the Zn2-2xCd2xV2O7 structure.The role of local symmetry in the formation of the non-autonomous phase is shown on the basis of X-ray diffraction studies in situ and a comparative crystal-chemical analysis of the structural deformations of isoform monoclinic solid solutions of zinc and copper pyrovanadates with zero volumetric thermal expansion.
Highlights
The non-autonomous phase is a phase whose existence under a certain thermodynamic conditions is possible only in an ensemble with one or more compounds
Previously unknown effect of a reversible transition from a single-phase system to a heterophase system; the latter, together with the main phase, contains the non-autonomous phase (NP)
The changes of unit cell parameters for the solid solutions within the temperature range from the room temperature up to 800 °C were analyzed (Fig. 2) in order to establish the relations between the appearance of non-autonomous phase in the Zn2V2O7 – Cd2V2O7 system and the transformations of the matrix phase
Summary
The non-autonomous phase is a phase whose existence under a certain thermodynamic conditions is possible only in an ensemble with one or more compounds. A precise high-temperature and low-temperature in situ X-ray diffraction studies of thermal expansion for a number of monoclinic β-Cu2–2xZn2xV2O7 (x = 0.15, 0.3, 0.4, 0.6) solid solution samples (space group C2/c) were performed in order to set the conditions for appearance and stabilization of the non-autonomous phase.
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