Electrical transport characteristics of ZnO-Bi2O3-B2O3 glasses

Optically clear glasses in the ZnO-Bi2O3-B2O3 (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz-10 MHz)-independent dielectric characteristics associated with significantly low loss (D = 0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18 +/- 4 ppm A degrees C-1 in the 35-250 A degrees C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi3+ cations in their own and different local environment.

Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

Conductivity studies on microwave synthesized glasses

Conductivity measurements have been made on x V O-2(5) - (100-x) 0.5 Na2O + 0.5 B2O3] (where 10 a parts per thousand currency sign x a parts per thousand currency sign 50) glasses prepared by using microwave method. DC conductivity (sigma) measurements exhibit temperature-and compositional-dependent trends. It has been found that conductivity in these glasses changes from the predominantly `ionic' to predominantly `electronic' depending upon the chemical composition. The dc conductivity passes through a deep minimum, which is attributed to network disruption. Also, this nonlinear variation in sigma (dc) and activation energy can be interpreted using ion-polaron correlation effect. Electron paramagnetic resonance (EPR) and impedance spectroscopic techniques have been used to elucidate the nature of conduction mechanism. The EPR spectra reveals, in least modified (25 Na2O mol%) glasses, conduction is due to the transfer of electrons via aliovalent vanadium sites, while in highly modified (45 Na2O mol%) glasses Na+ ion transport dominates the electrical conduction. For highly modified glasses, frequency-dependent conductivity has been analysed using electrical modulus formalism and the observations have been discussed.

Temperature and pressure dependence of direct current electrical resistivity in the Na2O-ZnO-B2O3 glass system

Two series of glasses were prepared, xNa2O, yZnO, 100 - x - yB2O3 and 30 - xNa2O, xZnO, 70B2O3 (mol%). The temperature dependence of the direct current resistivity was measured from room temperature to about 700 K and in both series of glasses we observed a simple Arrhenius type of temperature dependence. However, the resistivity of the binary alkali glass increased steeply by as much as two orders of magnitude with the addition of even a small quantity of ZnO and remained virtually unaffected by further addition of ZnO. The resistivity decreases gradually with increasing pressure in Na2O-B2O3 but increases with increasing pressure with the addition of ZnO.

Mössbauer effect and electron paramagnetic resonance studies on zinc borate glasses containing transition metal oxides

Studies have been carried out in glasses containing Fe2O3, V2O5, and Fe2O3 + V2O5. Mossbauer studies in the ZnO-B2O3-Fe2O3 system show that iron is present as Fe3+ with tetrahedral coordination and that the isomer shift and the quadrupole splitting decrease with increase of Fe2O3 Content; similarly, the isomer shift and quadrupole splitting are also found to decrease with increasing ZnO. On the other hand, in the Na2O-ZnO-B2O3-Fe2O3 system, the isomer shift increases with Na2O or ZnO while the quadrupole splitting is fairly insensitive. Electron paramagnetic resonance in the ZnO-B2O3-Fe2O3 system shows signals at g = 4.20 and 2.0, whose intensity and linewidth show strong dependence on Fe2O3 content. In the ZnO-B2O3-V2O5 system, electron paramagnetic resonance shows that vanadium is present as the vanadyl complex, and the hyperfine coupling constants, A(parallel-to) and A(perpendicular-to) decrease with increasing V2O5 content; on the other hand, g(parallel-to) decreases and g(perpendicular-to) increases slightly, indicating an increase in tetragonal distortion. Zinc borate glasses containing Fe2O3 + V2O5 do not show the hyperfine structure of V4+ due to the interaction between Fe3+ and V4+

The effect of host glass on optical absorption and fluorescence of Nd3+ in xNa(2)O-(30-x)K2O-70B(2)O(3) glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Nd3+ has been studied in mixed alkali borate glasses of the type xNa(2)O-(30-x)K2O-69.5B(2)O(3)-0.5Nd(2)O(3) (X = 5,10,15,20 and 25). Various spectroscopic parameters such as Racah (E-1, E-2 and E-3), spin-orbit (xi(4f)) and configuration interaction (alpha, beta) parameters have been calculated. The Judd-Ofelt intensity parameters (Omega(lambda)) have been calculated and the radiative transition probabilities (A(rad)), radiative lifetimes (tau(r)), branching ratios (beta) and integrated absorption cross sections (Sigma) have been obtained for certain excited states of the Nd3+, ion and are discussed with respect to x. From the fluorescence spectra, the effective fluorescence line widths (Deltalambda(eff)) and stimulated emission cross sections (sigma(p)) have been obtained for the three transitions F-4(3/2) --> I-4(9/2), F-4(3/2) --> I-4(11/2) and F-4(3/2) --> I-4(13/2) of Nd3+. The stimulated emission cross section (sigma(p)) values are found to be in the range (2.0-4.8) x 10(-2)0 cm(2) and they are large enough to indicate that the mixed alkali borate glasses could be potential laser host materials.

Optical Properties of Nanocrystalline Potassium Lithium Niobate in the Glass System (100-x) TeO2-x(1.5K(2)O-Li2O-2.5Nb(2)O(5))

Optically clear glasses of various compositions in the system (100-x) TeO2-x(1.5K(2)O-Li2O-2.5Nb(2)O(5)) (2 <= x <= 12, in molar ratio) were prepared by the melt-quenching technique. The glassy nature of the as-quenched samples was established via differential scanning calorimetry (DSC). The amorphous and the crystalline nature of the as-quenched and heat-treated samples were confirmed by the X-ray powder diffraction and transmission electron microscopic (TEM) studies. Transparent glasses comprising potassium lithium niobate (K3Li2Nb5O15) microcrystallites on the surface and nanocrystallites within the glass were obtained by controlled heat-treatment of the as-quenched glasses just above the glass transition temperature (T-g). The optical transmission spectra of these glasses and glass-crystal composites of various compositions were recorded in the 200-2500 nm wavelength range. Various optical parameters such as optical band gap, Urbach energy, refractive index were determined. Second order optical non-linearity was established in the heat-treated samples by employing the Maker-Fringe method.

Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

Elastic properties of phosphotungstate glasses

Elastic properties of potassium and lead phosphotungstate glasses have been investigated using ultrasonic velocity measurements. The composition dependence of elastic moduli in WO3-K2O-P2O5 glasses suggests that at low alkali oxide concentrations the atomic ring size increases by network modification, which results in the decrease of elastic moduli. In the highly modified regime, due to the presence of coulombic interaction, the rate of decrease of elastic moduli is reduced. In the WO3-PbO-P2O5 glasses the behaviour of elastic moduli suggests that PbO behaves both as a network former and network modifier. The incorporation of PbO into the network is quantitatively determined by the concentration of P2O5 in the system. The results are consistent with the structural model proposed earlier, based on characterization studies.

Electrical transport studies in alkali borovanadate glasses

The ac conductivity and dielectric behaviors of sodium borovanadate glasses have been studied over wide ranges of composition and frequency. The de activation energies calculated from the complex impedance plots decrease linearly with the Na2O concentration, indicating that ionic conductivity dominates in these glasses. The possible origin of low-temperature departures of conductivity curves (from linearity) of vanadium-rich glasses in log sigma versus 1/T plots is discussed. The ac conductivities have been fitted to the Almond-West type power law expression with use of a single value of s. It is found that in most of the glasses s exhibits a temperature-dependent minimum. The dielectric data are converted into moduli (M*) and are analyzed using the Kohlrausch-William-Watts stretched exponential function, The activation barriers, W, calculated from the temperature-dependent dielectric loss peaks compare well with the activation barriers calculated from the de conductivity plots. The stretching exponent beta is found to be temperature independent and is not likely to be related as in the equation beta = 1 - s, An attempt is made to elucidate the origin of the stretching phenomena. It appears that either a model of the increased contribution of polarization energy (caused by the increased modifier concentration) and hence the increased monopole-induced dipole interactions or a model based on increased intercationic interactions can explain the slowing down of the primitive relaxation in ionically conducting glasses.

A new approach for understanding ion transport in glasses; example of complex alkali diborate glasses containing lead, bismuth and tellurium oxides

Mechanism of ion transport in glasses continues to be incompletely understood. Several of the theoretical models in vogue fail to rationalize conductivity behaviour when d.c. and a.c. measurements are considered together. While they seem to involve the presence of at least two components in d.c. activation energy, experiments fail to reveal that feature. Further, only minor importance is given to the influence of structure of the glass on the ionic conductivity behaviour. In this paper, we have examined several general aspects of ion transport taking the example of ionically conducting glasses in pseudo binary, yNa(2)B(4)O(7)center dot(1-y) M (a) O (b) (with y = 0 center dot 25-0 center dot 79 and M (a) O (b) = PbO, TeO2 and Bi2O3) system of glasses which have also been recently characterized. Ion transport in them has been studied in detail. We have proposed that non-bridging oxygen (NBO) participation is crucial to the understanding of the observed conductivity behaviour. NBO-BO switching is projected as the first important step in ion transport and alkali ion jump is a subsequent event with a characteristically lower barrier which is, therefore, not observed in any study. All important observations in d.c. and a.c. transport in glasses are found consistent with this model.

Elastic Properties Of Sodium Borovanadate Glasses

The elastic properties of sodium borovanadate glasses have been studied over a wide range of composition using ultrasonic measurements. It is found that variation of different elastic moduli is very similar in any given series of composition. The bulk and shear moduli show a monotonic variation with the covalent bond energy densities calculated from the proposed structural model for these glasses. The bulk moduli also vary as a negative power function of the mean atomic volume. The Debye temperature varies linearly with the glass transition temperature. The implications of the observed behavior have been discussed.

Spectroscopic investigations of manganese ions in microwave-prepared NaPO3-PbO glasses

The EPR spectra of microwave-prepared 70NaPO(3):30PbO glasses containing different weight percentages of manganese ions have been studied. The EPR spectra exhibit a well-resolved hyperfine pattern at g(eff) approximate to 2.0. Optical absorption, fluorescent emission and excitation spectra of the glasses have been examined. The absorption spectrum exhibits a peak near 500 nm and this has been attributed to the spin-allowed E-5(g) --> T-5(2g) transition of Mn3+ ions. The emission spectrum shows a band at 595 nm which has been assigned to the T-4(1g)(G) --> (6)A(1g)(S) spin-forbidden transition of Mn2+ ions in octahedral coordination. Concentration quenching of fluorescence was found to occur above 0.75 wt% of Mn2+ ions. The excitation spectra exhibit four bands characteristic of Mn2+ ions in octahedral coordination. From the observed band positions of the excitation spectra, the crystal field parameter D-q and the Racah interelectronic repulsion parameters, B and C have been calculated. A structural model is proposed based on the IR, Raman and MASNMR studies according to which Mn2+ ions are likely to occupy sites similar to Na+ ions in these glasses.

Structural and lithium ion transport studies in sol-gel-prepared lithium silicophosphate glasses

Lithium silicophosphate glasses have been prepared by a sol-gel route over a wide range of compositions. Their structural and electrical properties have been investigated. Infrared spectroscopic studies show the presence of hydroxyl groups attached to Si and P. MAS NMR investigations provide evidence for the presence of different phosphatic units in the structure. The variations of de conductivities at 423 K and activation energies have been studied as a function of composition, and both exhibit an increasing trend with the ratio of nonbridging oxygen to bridging oxygen in the structure. Ac conductivity behavior shows that the power law exponent, s, is temperature dependent and exhibits a minimum. Relaxation behavior has been examined in detail using an electrical modulus formalism, and modulus data were fitted to Kohlraush-William-Watts stretched exponential function. A structural model has been proposed and the unusual properties exhibited by this unique system of glasses have been rationalized using this model. Ion transport in these glasses appears to be confined to unidimensional conduits defined by modified phosphate chains and interspersed with unmodified silica units.

Structural correlations in GexSe1-x glasses - a neutron diffraction study

Neutron diffraction measurement is carried out on GexSe1-x glasses, where 0.1 less than or equal to x less than or equal to 0.4, in a Q interval of 0.55-13.8 Angstrom(-1). The first sharp diffraction peak (FSDP) in the structure factor, S(Q), shows a systematic increase in the intensity and shifts to a lower Q with increasing Ge concentration. The coherence length of FSDP increases with x and becomes maximum for 0.33 less than or equal to x less than or equal to 0.4. The Monte-Carlo method, due to Soper, is used to generate S(Q) and also the pair correlation function, g(r). The generated S(Q) is in agreement with the experimental data for all x. Analysis of the first four peaks in the total correlation function, T(r), shows that the short range order in GeSe2 glass is due to Ge(Se-1/2)(4) tetrahedra, in agreement with earlier reports. Se-rich glasses contain Se-chains which are cross-linked with Ge(Se-1/2)(4) tetrahedra. Ge-2(Se-1/2)(6) molecular units are the basic structural units in Ge-rich, x = 0.4, glass. For x = 0.2, 0.33 and 0.4 there is evidence for some of the tetrahedra being in an edge-shared configuration. The number of edge-shared tetrahedra in these glasses increase with increasing Ge content.