Fluorite solid solutions of congruent melting in the PbF2–CdF2–RF3 systems

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Based on thermodynamic-topological analysis, the concentration regions for obtaining homogeneous crystals in the MF2–M'F2–RF3 systems (M≠M' = Ca, Sr, Cd, Ba and Pb, R = rare earth elements, REEs) were determined. Fluorite solid solution crystals in the PbF2–CdF2–RF3 systems (R = Tb, Ho, Er, Tm, Yb and Lu) were grown by the vertical directional crystallization technique. Their phase composition and distribution of components along the length of the crystalline boule were studied. Crystals of congruently melting solid solutions (Pb0.67Cd0.33)1–xRxF2+x (R = Tb, Ho, Er, Tm, Yb, Lu) were grown for the first time. In crystals with R = Ho, Er, Tm and Yb traces of low-temperature ordering of the solid solution were found – phase isostructural to the Pb2YF7 compound (sp. gr. I4/m), in which the Y positions are occupied by the corresponding R cations, and the Pb positions can be partially replaced Cd cations. Crystals with R = Tb and Lu have a high degree of homogeneity and are suitable for optical research.

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作者简介

I. Buchinskaya

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

编辑信件的主要联系方式.
Email: buchinskayii@gmail.com
俄罗斯联邦, Moscow

P. Fedorov

A.M. Prokhorov General Physics Institute of the Russian Academy of Sciences

Email: buchinskayii@gmail.com
俄罗斯联邦, Moscow

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2. Fig. 1. Block diagram of the state diagrams of binary systems formed by fluorite difluorides of alkaline earth metals, MF2–MF2 (M = Ca, Sr, Cd, Ba, Pb)

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3. Fig. 2. The main types of liquid–solid state diagrams for ternary systems with continuous solid and liquid solutions: in the absence of congruent points on the melting surfaces (a) and in their presence – maximum (b), minimum (c) and saddle (d). The upper row schematically shows the shapes of the surfaces, in the middle – the general view of the T–x diagrams, in the lower - the projections of the liquidus surface (lines – isotherms)

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4. Fig. 3. Compositions of saddle points on concentration triangles for series of systems CaF2–SrF2–RF3 (a), BaF2–SrF2–RF3 (b) and PbF2–CdF2–RF3 (c)

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5. Fig. 4. Example of crystal beads “as grown”

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6. Fig. 5. Distribution of cations along the length of crystal beads for R = Tb (a), Ho(b), Er(c), Tm (d), Yb(e) and Lu(e). The inserts show examples of plates cut from crystals and illuminated for optical viewing

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7. Fig. 6. The general picture of the diffractograms Pb1–x–yCdxRyF2+y (R = Tb, Ho–Lu) (a). The enlarged area of the diffractograms near the background for R = Ho–Yb (b). The barcode diagrams of the Pb2YF7 compound (gr. I4/m) are shown above, PDF No. 00-037-1116, and the cubic phase of the sample Pb0.49Cd0.24Yb0.27F0.27 (etc. gr. Fm3m)

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