Structural and impedance spectroscopic investigations of eco-friendly alkali phosphoborate glass-ceramics containing zirconium ion.

Glass-ceramics with novel composition xZrO2.7P2O5.19CaO.24Na2O.(50-x)B2O3 (x = 0, 2, 4, 6, and 8 mol%) have been synthesized using melt quench technique. The synthesized compositions were characterized and analyzed by X-ray diffraction, field emission scanning electron microscopy, infrared absorption, and impedance spectroscopy. X-ray diffraction profiles of prepared samples confirm the existence of phases corresponding to Na3Ca6(PO4)5 crystal (with crystallite size ~ 23 nm). Infrared absorbance spectra reveal the presence of phosphate and borate units (PO3, PO4, BO3, BO4) in the glass matrix. Different dielectric parameters such as dielectric loss, electric modulus, and tangent loss were evaluated. Their variations with temperature and frequency confirm the non- Debye relaxation behavior of prepared samples. A phenomenal description of the capacitive behavior was studied by considering the circuit having a parallel combination of constant phase element and bulk resistance. The conduction is found to be governed by overlapping large polaron tunneling (OLPT) and follow OLPT model. The results indicate that ZrO2 substituted alkali phosphoborate glass-ceramics can be used as eco-friendly and safe dielectric materials.

EPR and impedance spectroscopic investigations on lithium bismuth borate glasses containing nickel and vanadium ions.

Glasses having composition 7NiO∙23Li2O∙20Bi2O3∙50B2O3, 7V2O5∙23Li2O∙20Bi2O3∙50B2O3 and x(2NiO∙V2O5)∙(30-x)Li2O∙50B2O3∙20Bi2O3 (with x=0, 2, 5, 7 & 10 mol%) prepared through melt-quench route are explored by analyzing density, impedance spectroscopy and electron paramagnetic resonance (EPR). It is found that both density and molar volume increase with an increase in substitution of 2NiO∙V2O5 in the base glass matrix. Different dielectric parameters viz. dielectric loss (ε), electrical modulus (M), loss tangent (tanδ) etc. are evaluated and their variations with frequency and temperature are analyzed which reveals that these glasses exhibit a non-Debye relaxation behavior. A phenomenal description of the capacitive behavior is obtained by considering the circuitry as a parallel combination of bulk resistance (Rb) and constant phase element (CPE). The conduction mechanism is found to follow Quantum Mechanical Tunneling (QMT) model. Spin Hamiltonian Parameters (SHPs) and covalency rates are calculated from the EPR spectra of vanadyl ion. The observed EPR spectra confirmed that V(4+) ion exists as vanadyl ion in the octahedral coordination with tetragonal compression.