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PbOSb2O3As2O3 glasses mixed with different concentrations of MnO (ranging from 0 to 5.0 mol%) were crystallized. The samples were characterized by X‐ray diffraction, scanning electron microscopy and differential thermal analysis techniques. Dielectric properties over a range of frequency and temperature, optical absorption, fluorescence IR, ESR and magnetic susceptibility at room temperature have been studied. The X‐ray diffraction studies have revealed the presence of Pb5Sb2O8, PbSb2O6, SbAsO4, Mn2Sb2O7, Mn3Sb2O6, Mn2O3, MnAsO4 and Pb5Sb4O11 crystalline phases in these samples. The DTA studies have indicated the spreading of the crystallization from inside to the surface of the samples as the concentration of the crystallizing agent is increased. The IR studies have pointed out the existence of conventional AsO3 and SbO3 structural units in the glass ceramic samples. These studies have further indicated the decreasing concentration of symmetrical structural vibrational groups with increase in the concentration of MnO. The results of various studies viz., also been reported. The results of optical absorption, ESR, luminescence and magnetic susceptibility studies have been analysed in the light of different oxidation states and environment of manganese ions in the glass ceramic network.

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