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  • Author or Editor: V. Pet’kov x
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Abstract  

Data on synthesis, thermal behavior and thermodynamic properties for the NZP phosphates NaMe2(PO4)3 and Na5Me(PO4)3 (Me=Ti, Zr, Hf) are reported. The compounds were synthesized by sol-gel method and solid-state reactions and characterized by X-ray powder diffraction, IR spectroscopy, electron microprobe and chemical analysis. Their thermal behavior was studied by the DTA measurements. The heat capacities of the phosphates were measured between temperatures 7 and 650 K. The fractal dimensions for the phosphates were calculated. The obtained thermodynamic characteristics of these phosphates and also literature data for the compounds of NZP type structure are summarized.

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Abstract  

A5–4xZrxZr(PO4)3 (A=Na, K;0≤x≤1.25), Na1-xCd0.5xZr2(PO4)3 (0≤x≤1), Na5–xCd0.5xZr(PO4)3 (0≤x≤4) compositions which belong to the NZP structural family were synthesized using the sol-gel method. The lattice thermal expansion of members of these rows were determined up to 600C by high-temperature X-ray diffractometry. The axial thermal expansion coefficients change from -5.810-6to 7.510-6 C-1a) and from 2.610–6 to 2210–6 C-1c). These results, in addition to those for other NZP compounds allow us to explain their low thermal expansion. The mechanism can be attributed to strongly bonded three-dimensional network structure, the existence of structural holes capable to damp some of the thermal vibrations and anisotropyin the thermal expansion of the lattice.

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Abstract

The temperature dependence of the heat capacity of crystalline barium zirconium phosphate C p o = f(T) was measured over the temperature range 6–612 K. The experimental data obtained were used to calculate the standard thermodynamic functions C p o(T), H°(T) − H°(0), S°(T), G°(T) − H°(0) over the temperature range from T → 0 to 610 K and standard entropy of formation at 298.15 K. The data on the low-temperature (6 ≤ T/K ≤ 50) heat capacity were used to determine the fractal dimension of Ba0.5Zr2(PO4)3. Conclusions concerning the topology of the structure of phosphate were drawn. Thermodynamic properties of M0.5Zr2(PO4)3 (M = Ca, Sr, Ba) were compared.

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Journal of Thermal Analysis and Calorimetry
Authors:
V. I. Pet’kov
,
E. A. Asabina
,
A. V. Markin
,
N. N. Smirnova
, and
D. B. Kitaev

Summary The thermodynamic data for NZP compounds MZr2(PO4)3 (M=Na, K, Rb, Cs, Zr0.25) and Na5D(PO4)3 (D=Ti, Zr) are reported. The heat capacities of the phosphates were measured between T=7 and T=640 K. The standard enthalpies entropies, and Gibbs functions of formation at T=298.15 K were derived. The obtained thermodynamic characteristics of phosphates of the NZP type structure and literature data are summarized. Thermodynamic functions of reactions of solid-state synthesis were calculated and the usability of ceramic technology for obtaining NZP compounds was proved.

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