The network modifier and former role of the bismuth ions in the bismuth-lead-germanate glasses.

The present work is focused on the enhancement of network former environment in lead-germanate glasses by bismuth ions doping. A series of bismuth-lead-germanate glasses with the xBi2O3·(100-x)[7GeO2·3PbO] composition glass where 0≤x≤30 mol% Bi2O3 were synthesized by melt-quenching method. The FTIR, UV-VIS spectroscopy and cyclic voltammetry were conducted on these samples to evaluate the doping effect of structure of the host matrix network. Our results indicate that direct incorporation of Bi2O3 into the lead-germanate network modifies the lead-germanate network and the internal structure of glass network is rearranged. The structural flexibility of the lead-germanate network is possible due to its incapacity to accommodate with the excess of oxygen atoms and the creation of bridging oxygen ions. Optical gap energy and refractive index were obtained as a function of Bi2O3 content. Gap energy values decrease as Bi2O3 content increased from 0 to 10 mol%. Further increase of Bi2O3 concentration beyond 10 mol% increased the gap energy values. These behaviors of the glass system can be explained by two mechanisms: (i) for x≤10 mol% Bi2O3--increase of degree of disorder of the host matrix because Bi2O3 is network modifier and (ii) for x>10 mol%--Bi2O3 acts as a network former. Cyclic voltammetry measurements using the glass system with 10Bi2O3·90[7GeO2·3PbO] composition as working electrode show the mobility of the lead ions, in agreement with UV-VIS data.

Effect of aluminum oxide codoping on copper-lead-germanate glasses.

Glasses from xCuO⋅(100-x)[7GeO(2)⋅3PbO(2)⋅0.05Al(2)O(3)] system where x=0, 1, 5, 10, 20 and 30 mol% CuO were studied by FT-IR, UV-VIS and ESR spectroscopy in order to obtain information about the structural correlations and the relationship between structure and optical properties in these materials. The analyses of these IR spectra reveal that the accommodation of the network with the excess of oxygen ions is possible by the depolymerization of the germanate network in shorter chains, especially ortho- and/or pyrogermanate structural units. UV-VIS absorption spectrum of the sample with x=1% CuO begins with a rising absorption band situated at about 250 nm. This band can be assigned to the GeOGe wrong bonds such as the Ge(+2) centers. Optical study is performed to calculate the refractive index and optical band gap using UV-VIS spectra in the wavelength range 250-1,000 nm. The increase in optical band is explained on the basis of the average bond energy of the system and the number of non-bridging oxygen ions. ESR spectra of CuO substituted samples are characterized by broad peaks probably because of the formation of Cu(+2)-Ge(+2) exchange pairs which are weakly coupled though the oxygen atom.