Synthesis and characterization of thorium phosphate phases by spray pyrolysis: chemistry of thorium phosphates

This paper describes the synthesis of some thorium phosphate compounds with different Th/P ratio (1/2, 2/3 and 3/4) by a spray pyrolysis technique. The so-prepared rough compounds were annealed at different temperatures for 2 h and then analyzed by mainly X-ray diffraction on powder and infrared spectroscopy. Every rough compound is composed by very badly crystallized ThO₂ phase polluted by carbon residue. An annealing treatment at 800 °C leads to the thorium diphosphate phase, α-ThP₂O₇ in every case. At 900 °C, such a phase is decomposed into a thorium phosphate diphosphate phase (Th₄(PO₄)₄P₂O₇, called TPD). However, a thorium excess in the initial mixture (Th/P = 3/4) leads also to observe the ThO₂ phase. The TPD phase is stable up to 1200 °C and does not react with the ThO₂ compound. Beyond 1200 °C, the TPD phase is slowly decomposed into a thorium phosphate compound which should be a thorium oxide phosphate; this compound does not contain any diphosphate species.