Phase Diagram and Metastable Phases in the LaPO4–YPO4–(H2O) System

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Abstract

Phase formation in the LaPO4-YPO4-(H2O) system was studied under hydrothermal conditions at T≈230°C and after thermal treatment in the temperature range 1000–1400°C. The phase equilibrium diagram was constructed for the LaPO4-YPO4 system. The regions of metastable binodal and spinodal phase transition monazite-structured with a critical point Tcr = 931°C have been calculated. The experimentally determined eutectic temperature of 1850±35°C is in good agreement with the calculated value Te=1820°C. The maximum solubility of YPO4 in LaPO4 at eutectic temperature obtained from the thermodynamic optimized phase diagram is 50.5 mol.%.

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About the authors

M. O. Enikeeva

Ioffe Institute; Saint Petersburg State Institute of Technology

Author for correspondence.
Email: odin2tri45678@gmail.com
Russian Federation, Saint Petersburg; Saint Petersburg

O. V. Proskurina

Ioffe Institute; Saint Petersburg State Institute of Technology

Email: odin2tri45678@gmail.com
Russian Federation, Saint Petersburg; Saint Petersburg

V. V. Gusarov

Ioffe Institute

Email: odin2tri45678@gmail.com
Russian Federation, Saint Petersburg

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Supplementary files

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2. Fig. 1. Diffractograms of samples obtained by the deposition method: 1, 2 and 3 - designations of reflexes with the structure of rhabdophane, cherchite and xenotime, respectively.

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3. Fig. 2. Dependence of the change in the unit cell volume attributed to one formula unit (V/z) in the structures of rhabdophane (1), cherchite (2) and xenotime (3) on the YPO4 content in the system.

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4. Fig. 3. The ratio of the number of phases in the LaPO4-YPO4 system after annealing at 1000C for 7 days depending on the YPO4 content (x, mol. d.) in the system (a) and the dependence of the unit cell volume attributed to one formula unit of the structure (V/z) on the YPO4 content (x, mol. d.) in the system for the structures: 1, 1′ - monazite, 2 - xenotime (b).

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5. Fig. 4. The ratio of the number of phases in the LaPO4-YPO4 system after annealing at 1200С for 5 days depending on the YPO4 content (x, mol. d.) in the system (a) and the dependence of the unit cell volume attributed to one formula unit of the structure (V/z) on the YPO4 content (x, mol. d.) in the system for the structures: 1, 1′ - monazite, 2 - xenotime (b).

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6. Fig. 6. The ratio of the number of phases in the LaPO4-YPO4 system after annealing at 230С for 28 days depending on the YPO4 content (x, mol. d.) in the system (a) and the dependence of the unit cell volume attributed to one formula unit of the structure (V/z) on the YPO4 content (x, mol. d.) in the system for the structures: 1 - monazite, 2 - xenotime (b).

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7. Fig. 7. (a) State diagram of LaPO4-YPO4 system. Solid curve - thermodynamically optimized phase equilibria diagram, dashed curve - metastable binodal - hypothetical delamination of the phase with monazite structure, dot-dashed curve - spinodal decomposition of the phase with monazite structure. Experimental data: 1 - single phase composition with monazite structure, 2 - equilibrium composition based on the phase with monazite structure, 3 - equilibrium composition with xenotime structure, 4 - bulk composition of samples in the two-phase region, 5 - melting onset temperature of the solid phase determined by the WPA method. Calculated data: 6 - points of metastable binodal decay for the phase with monazite structure at 600C, 7 - points of spinodal decay for the phase with monazite structure at T = 600C. (b) Molar Gibbs mixing energy curve of the phase with monazite structure with a common tangent to the curve: x - mol. d. YPO4, GmM,Mon - molar Gibbs mixing energy of the phase with monazite structure (subregular model), J/mol.

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