ABSTRACT
Glasses with composition 15Li(2)O-15K(2)O-xBi(2)O(3)-(65 - x)-B(2)O(3)/5V(2)O(5) (3 ≤ x ≤ 15) have been prepared by the conventional melt quench technique. The electron paramagnetic resonance spectra of VO(2+) in these glasses have been recorded in the X-band frequency (≈9.3 GHz) at room temperature. The spin Hamiltonian parameters and covalency rates were evaluated. It was found that the V(4+) ions exist as vanadyl (VO(2+)) ions and are in an octahedral coordination with a tetragonal compression. The covalency rates (1 - α(2)) and (1 - γ(2)) indicate moderate covalency for the σ- and π-bonds. It was observed that the spin-Hamiltonian parameters depend slightly on the relative concentration of Bi(2)O(3). The optical properties of this glass system are studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The direct current electrical conductivity, σ, has been measured in the temperature range 373-573 K. The conductivity decreases with the increase in Bi(2)O(3) concentration. This has been discussed in terms of the decrease in the number of mobile ions and their mobility. An attempt is made to correlate the EPR, optical, and electrical results and to find the effect of Bi(2)O(3) content on these parameters.
ABSTRACT
A lithium-potassium-borate glass system containing manganese and iron cations has been thoroughly investigated in order to obtain information about the mixed alkali effect and the structural role of both the manganese and iron in such glass hosts. Mixed alkali borate glasses of the (30 - x)Li(2)O - xK(2)O - 10CdO/ZnO - 59B(2)O(3) (x = 0, 10, 15, 20, and 30) doped with 1MnO(2)/1Fe(2)O(3) system were prepared by a melt quench technique. The amorphous phase of the prepared glass samples was confirmed from their X-ray diffraction. The spectroscopic properties of glass samples were studied using infrared (IR) and Raman spectroscopic techniques. The density of all the prepared glasses was measured using Archimedes principle. Molar volumes were estimated from the density data. IR spectra of these glasses revealed a dramatic variation of three- and four-coordinated boron structures as a function of mixed alkali concentration. The vibrations due to Li-O, K-O, and MnO(4)/FeO(4) arrangements are consistent in all the compositions and show a nonlinear variation in the intensity with alkali content. Raman spectra of different alkali combinations with CdO and ZnO present drastic changes in the intensity of various Raman bands. The observation of disappearance and reappearance of IR and Raman bands as a function of various alkali concentrations is an important result pertaining to the mixed alkali effect in borate glasses. Acting as complementary spectroscopic techniques, both types of measurements, IR and Raman, revealed that the network structure of the studied glasses is mainly based on BO(3) and BO(4) units placed in different structural groups, the BO(3) units being dominant. The measured IR and Raman spectra of different glasses are used to clarify the optical properties of the present glasses correlating them with their structure and composition.
