Investigations of potassium-cerium phosphates rich in P2O5

In the ternary system Ce₂O₃-K₂O-P₂O₅, the partial system Ce(PO₃)₃-KPO₃-P₂O₅ was examined by means of differential thermal analysis and powder X-ray diffraction. The phase compositions of the products obtained on various thermal treatments were investigated. The phase diagram of the system Ce(PO₃)₃-KPO₃-P₂O₅ is suggested.

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Zusammenfassung Mittels DTA und Röntgendiffraktion wurde im ternären System Ce₂O₃-K₂O-P₂O₅ das Teilsystem Ce(PO₃)₃-KPO₃-P₂O₅ untersucht. Die Phasenzusammensetzungen der durch verschiedene Erhitzungsvorgänge erhaltenen Produkte wurden untersucht und ein Phasendiagramm für das System Ce(PO₃)₃-KPO₃-P₂O₅ erstellt.

     

The synthesis and thermal stability of cerium ultraphosphate CeP5O14

The synthesis and thermal stability of cerium ultraphosphate CeP₅O₁₄ were examined by differential thermal analysis, powder X-ray diffraction, microscopy (electron microscope) and IR spectroscopy.

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Zusammenfassung Mittels DTA, Debye-Scherrer-Untersuchungen, Mikroskopie (Elektronenmikroskopie) und IR-Spektroskopie wurde die Synthese und thermische Stabilität von Zer-ultraphosphat CeP₅O₁₄ untersucht.

     

The system KPO3-Y(PO3)3

The previously unknown binary system KPO₃-Y(PO₃)₃ has been examined by thermal, X-ray and microscopic analysis and its phase diagram provided. The existence of the compound KY(PO₃)₄ has been confirmed. Its melting point (700°, incongruent) and basic parameters of the unit cell (monoclinic system, space group P2_1/n, lattice parameters: a=7.36, b=8.36, c=14.39 Å, =96.1°) have been determined. The new, so far unknown, compound has been discovered and assigned the formula K₂Y(PO₃)₅. It has been found that it forms peritectoidally (in the solid phase) at 642°.

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Zusammenfassung Das zuvor unbekannte binäre System KPO₃-Y(PO₃)₃ wurde mittels Thermo-, Röntgendiffraktions- und mikroskopischer Analyse untersucht und das Phasendiagramm aufgestellt. Die Existenz der Verbindung KY(PO₃)₄ wurde dabei bekräftigt. Ihr Schmelzpunkt (700°, inkongruent) und die grundlegenden Parameter der Elementarzellen (monoklines System, Raumgruppe P2_1/n, Gitterkonstanten: a=7.36, b=8.36, c=14.39 Å, =96.1°) wurden ermittelt. Weiterhin wurde eine neue, bislang unbekannte Verbindung mit der Formel K₂Y(PO₃)₅ entdeckt. Sie verfügt (in fester Phase) über ein Peritektikum bei 642°.

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This paper was included in the CPBP-01.18 problem and was financially supported by the Ministry of National Education.     

Phase equilibria in the Ce<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Ce₂O₃-K₂O-P₂O₅ ternary system has been investigated by thermoanalytical methods (DTA, DSC), powder X-ray diffraction, XPS and IR spectroscopy. The existence of three double potassium-cerium(III) phosphates has been confirmed and a new binary phosphate K₄Ce₂P₄O₁₅ has been found. Phase diagram and isothermal section at room temperature of the system Ce₂O₃-K₂O-P₂O₅ have been presented.     

The system Mg2P2O7−Na8Mg6(P2O7)5−NaPO3−Mg(PO3)2

Phase equilibria in the partial system Mg₂P₂O₇?Na₈Mg₆(P₂O₇)₅?NaPO₃?Mg(PO₃)₂ were examined by differential thermal analysis and powder X-ray diffraction. It was found that there are six sections in the composition range under investigation.     

Phase equilibria in the oxide system Nd2O3–K2O–P2O5

A phase equilibria diagram of the partial system NdPO₄–K₃PO₄–KPO₃ has been developed as part of the research aimed at determining the phase equilibrium relationships in the oxide system Nd₂O₃–K₂O–P₂O₅. The investigations were conducted using thermoanalytical techniques, X-ray powder diffraction analysis and reflected-light microscopy. Three isopleths existing between: K₃Nd(PO₄)₂–K₄P₂O₇, NdPO₄–K₅P₃O₁₀ and NdPO₄–K₄P₂O₇ have been identified in the partial NdPO₄–K₃PO₄–KPO₃ system. Previously unknown potassium-neodymium phosphate “K₄Nd₂P₄O₁₅” has been discovered in the latter isopleth section. This phosphate exists in the solid phase up to a temperature of 890 °C at which it decomposes into the parent phosphates NdPO₄ and K₄P₂O₇. Four invariant points: two quasi-ternary eutectics, E₁ (1057 °C) and E₂ (580 °C) and two quasi-ternary peritectics, P₁ (1078 °C) and P₂ (610 °C), occur in the NdPO₄–K₃PO₄–KPO₃ region.     

Phase equilibria in the system Rb3PO4–Ba3(PO4)2

The system Rb₃PO₄–Ba₃(PO₄)₂ was investigated by thermoanalytical methods, X-ray powder diffraction, ICP, and FT-IR. On the basis of the obtained results its phase diagram was proposed. For this system with one intermediate compound, BaRbPO₄, we found that this compound melts congruently at 1700 °C, exhibits a polymorphic transition at 1195 °C and is high-temperature unstable. Also, the intermediate compound was subject to gradual decomposes to Ba₃(PO₄)₂ (the solid phase) and vaporization (with conversion of phosphorus and rubidium oxides into vapor phase). We also found that Rb₃PO₄ melts congruently at 1450 °C and shows a polymorphic transition at 1040 °C. Regarding Ba₃(PO₄)₂, we have confirmed that it melts congruently at 1605 °C and exhibits a polymorphic transition at 1360 °C.     

Investigation of phase equilibria in the Er2O3–Na2O–P2O5 system: the partial system ErPO4–NaPO3–Er(PO3)3

The partial system ErPO₄–NaPO₃–Er(PO₃)₃ of the Er₂O₃–Na₂O–P₂O₅ oxide system has been investigated by thermoanalytical methods and X-ray powder diffraction. On the basis of the obtained results the phase diagram of the partial system is proposed. The system is bounded by three subsystems: (i) ErPO₄–Er(PO₃)₃, (ii) Er(PO₃)₃–NaPO₃ and (iii) ErPO₄–NaPO₃. Their phase diagrams are proposed. In the Er(PO₃)₃–NaPO₃ subsystem an intermediate compound NaEr(PO₃)₄ occurs; it melts incongruently at 655 °C. It was found that ErPO₄ and NaEr(PO₃)₄ form a section which is a real system only in the subsolidus region (below 646 °C). Two ternary invariant points (one ternary peritectic and one ternary eutectic) occur in the investigated partial system ErPO₄–NaPO₃–Er(PO₃)₃.     

Phase equilibria in the YPO4–Rb3PO4 system

The phase equilibria occurring in the YPO₄–Rb₃PO₄ system were investigated by thermoanalytical methods, X-ray powder diffraction, and ICP-OES. On the basis of the obtained results, its phase diagram is proposed. It was found that the system includes two intermediate compounds Rb₃Y(PO₄)₂ and Rb₃Y₂(PO₄)₃. The Rb₃Y(PO₄)₂ compound melts congruently at 1300 °C. The Rb₃Y₂(PO₄)₃ orthophosphate was previously unknown. This intermediate compound is high-temperature unstable and decomposes within the temperature range 1300–1330 °C to YPO₄ and Rb₃Y(PO₄)₂. The decomposition process is irreversible. It was found that the Rb₃Y₂(PO₄)₃ orthophosphate is isostructural with Rb₃Yb₂(PO₄)₃ and crystallizes in the cubic system (a = 1.70226 nm).