Structural and Calorimetric Studies of Zinc, Magnesium and Manganese Based Phosphate and Phosphate-Silicate Glasses

Abstract

Glasses of the (50-x/2)Na 2 O-xMO-(50-x/2)P 2 O 5 (M = Zn, Mg or Mn) (0 ≤ x ≤ 33 mol%), (50-x)Na 2 O-xMO-50P 2 O 5 (M = Zn, Mn) (0 ≤ x ≤ 33 mol%), and (0.9-x) NaPO 3 -xSiO 2 -0.1ZnO (0 ≤ x ≤ 0.1 mol) were prepared by the melt quenching technique. Samples were investigated by means of X-ray diffraction, Archimede's method, ellipsometry, Fourier-transformed infrared (FTIR), Raman, 31P solid state magic angle spinning nuclear magnetic resonance (MAS-NMR), UV-visible spectroscopy and calorimetry. For zinc, manganese and magnesium phosphate glasses, the increase in density with the addition of MO oxide suggests the compactness of the vitreous network. For zinc phosphate silicate glasses, the variations of density and refractive index were attributed to the structural changes when SiO 2 oxide is progressively introduced. The increase in the glass transition temperature (Tg) reflects an increase in the cross-link strength of the structure as MO and SiO 2 oxides are gradually incorporated. For all glass composition, spectroscopic investigations revealed the depolymerization of metaphosphate chains (Q 2 ) allowing the formation of phosphate dimers (Q 1 ). Calorimetric dissolution shows that the dissolution is endothermic for lower MO content and become exothermic when x rises. For (50-x/2)Na 2 O-xZnO-(50-x/2)P 2 O 5 (0 ≤ x ≤ 33 mol%) glasses, the formation enthalpy increases with the incorporation of ZnO oxide.

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“…Generally, these variations are related to modifications in the type of bonding in the vitreous network [ 28 ]. Glass transition and crystallization temperatures are principally related to the ionic field strength (IFS) of the cation introduced in the glass matrix [ 29 ].…”

“…Table 2 presents the variations of the glass transition temperature T g , the crystallization temperature T c,on , and the melting temperature T m of the prepared glasses with the amount of K 2 O for (CaO+MgO) substitution. Generally, these variations are related to modifications in the type of bonding in the vitreous network [28]. Glass transition and crystallization temperatures are principally related to the ionic field strength (IFS) of the cation introduced in the glass matrix [29].…”