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Synthesis, structural characterization and ionic conductivity of mixed alkali titanium phosphate glasses

Fatima Ezzahraa Dardar, Michael Gross, Saida Krimi, Michel Couzi, Abdessadek Lachgar, Said Sebti, Abdelaziz El Jazouli


Glasses with formula Na3-xLixCaTi(PO4)3 [10(3-x) mol. % Na2O - 10x mol. % Li2O - 20 mol. % CaO - 20 mol. % TiO2 - 30 mol. % P2O5] (0 ≤ x ≤ 3) were prepared by standard melt-quenching technique, and their structural and physical properties were characterized by thermal analysis, density measurements, Raman, and impedance spectroscopy. When Na+ is gradually replaced by Li+, molar volume, glass transition temperature (Tg) and ionic conductivity values decrease, pass through a minimum around the composition x = 1.5, then increase, while density values increase, pass through a maximum, then decrease. The non-linear variation of these physical properties is a result of the classical mixed alkali effect. Powder X-ray diffraction shows that crystallization of the glasses leads to the formation of a Nasicon phase for the compositions x = 0 and x = 0.5, and to a mixture of phases for the other compositions. Raman spectroscopy study shows that the glass structure contains P2O7 and PO4 groups, and short -Ti-O-Ti-O-Ti- chains, formed by TiO6 octahedra linked to each other through corners. These chains are linked by phosphate tetrahedra to form -O-Ti-O-P-O- linkages.

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