Ion dynamics in mixed alkali cadmium fluoride glasses

We have investigated ion dynamics in cadmium fluoride nonoxide glasses, in the frequency range from 10 Hz to 2 MHz and in the temperature range from room temperature to just below the glass transition temperature. We have established the existence of mixed alkali effect for these glasses from different aspects of relaxation dynamics. We have observed lower dimensionality of the conduction pathways in mixed alkali cadmium fluoride glasses compared to that in the single alkali glasses. Although, both n and beta represent the interaction between the charge carriers, we have not found any theoretical correlation between them. Using different scaling approaches we have shown that the relaxation dynamics in mixed alkali cadmium fluoride glasses is independent of temperatures.     

Correlation of ion dynamics and structure of superionic tellurite glasses

Ion dynamics and structure of a series of superionic AgI-doped silver tellurite glasses have been investigated in this paper. The composition dependence of the dc conductivity and the activation energy of these glasses has been compared with those of AgI-doped silver phosphate and borate glasses. We have observed that the conductivity increases and the activation energy decreases with increase of AgI content and that the tellurite glasses have higher conductivity than those for phosphate or borate glasses. We have analyzed the ac electrical data in the framework of the power law and the electric modulus formalisms. We have established a correlation between the crossover rate of the mobile silver ions and the rearrangement of the structural units in tellurite glasses. The scaling of the conductivity spectra has been used to interpret the temperature and composition dependence of the relaxation dynamics. Analysis of the dielectric relaxation in the framework of modulus formalism indicates an increase in the ion-ion cooperation in the glass compositions with increasing AgI content.     

Relaxation dynamics of Ag4Te3O8 glass nanocomposites embedded with Ag2S nanoparticles

Stable beta-Ag2S nanocrystals were dispersed in the Ag4Te3O8 glass network. These beta-Ag2S nanocrystals modified the tellurite network by rupturing the Te-O-Te linkages in the tellurite matrix. This structural modification was found to be different from that of the AgI doped silver tellurite glasses. The presence of beta-Ag2S nanoparticles was confirmed from the transmission electron micrographs. The structural modification was observed in the Fourier transform infrared spectra of the composites. Electrical properties for these composites were investigated in the temperature range of 125-303 K and in the frequency range of 10 Hz-2 MHz and were compared with those of the AgI doped silver tellurite glass system to shed some light on the influence of Ag2S nanoparticles on the ionic conduction and relaxation in the silver tellurite nanocomposites. The ionic relaxation in this system was also investigated using the electrical modulus formalism. Formation of nanocrystal in this nanocomposite system left some signature on the frequency exponent, crossover frequency, and the relaxation frequency, which became clear when compared with those of the silver tellurite glasses.     

Dynamics of lithium ions in bismuthate glasses: influence of strontium ions

The influence of strontium ions on the relaxation dynamics of lithium ions in bismuthate glasses has been investigated in the frequency range of 10 Hz to 2 MHz. We have observed that the conductivity increases and the activation energy decreases with the increase of SrO content in the glass compositions with fixed Li2O content. We have also observed that the conductivity increases and the activation energy decreases when Sr2+ ions are replaced by Li+ ions, keeping the glass former content fixed. We have shown that the estimated mobile ion concentration is almost independent of temperature and SrO content in the compositions. We have further shown that a fraction of total lithium ions are mobile for all glass compositions. The results have been interpreted on the basis of the modification of the bismuthate network by the addition of SrO, which enhances the mobility of Li ions, without altering the mobile Li+ ion concentration. We have also shown that the conductivity relaxation in these glasses is independent of temperature and composition, and the nonexponential parameter is less than that for the lithium bismuthate glasses without SrO.     

Dynamics of Li+ ions in strontium metaphosphate glasses

Dynamics of Li+ ions in strontium metaphosphate glasses has been studied in the frequency range of 10 Hz-2 MHz and in the temperature range of 273-573 K. The dc conductivity increases and the activation energy decreases with the replacement of strontium ions by lithium ions in the glass compositions. The ac electrical data have been studied using the modulus and conductivity formalisms. We have observed that the stretching exponent decreases and the frequency exponent increases with the replacement of strontium ions by lithium ions in these glasses. The variation of these parameters was explained in terms of ion-ion interaction. The mobile ion concentration remains nearly constant, which indicates that the mobility of the migrating ions increases when the alkaline earth ions are replaced by the alkali ions.     

Dynamics of lithium ions in calcium bismuthate glasses

Ion transport in Li(2)O-CaO-Bi(2)O(3) glasses has been studied in the frequency range from 10 Hz to 2 MHz and in the temperature range from 293 to 543 K. The variation of the dc conductivity and the activation energy of these glasses with composition have been compared with those of binary lithium bismuthate glasses. It has been observed that the introduction of CaO in small amount does not effect the dc conductivity and the corresponding activation energy, but the larger amount of CaO changes them to some extent. The frequency-dependent conductivity has been studied using both conductivity and modulus formalisms. The values of the nonexponential parameter and frequency exponent are found to differ for the Li(2)O-CaO-Bi(2)O(3) glasses from those for the binary Li(2)O-Bi(2)O(3) glasses. The concentration of mobile Li(+) ions does not change appreciably with the change in the Li(2)O as well as CaO content in the compositions. The increasing amount of CaO in the glass compositions for fixed Li(2)O content points out that CaO dilates the glass network, enhancing the migration of Li(+) ions.     

Dynamic light scattering in mixed alkali metaphosphate glass forming liquids

We report the first ever photon correlation spectroscopy performed on single alkali and mixed alkali metaphosphate glasses at refractory temperatures above the glass transition. We find not only a significant decrease in the glass transition temperature but also a decrease in fragility for the mixed alkali composition as compared with the single akali glasses. We argue that structural relaxation in these polymeric oxide glasses is largely controlled by the cross linking cations and that the changes in fragility that we observed are a reflection of changes in the cooperativity of structural relaxation wrought by the substantial decrease in the ion mobility that accompanies the mixing of alkali ions.     

Relaxation dynamics in AgI-doped silver vanadate superionic glasses

Relaxation dynamics of Ag+ ions in several series of AgI-Ag2O-V2O5 superionic glasses has been studied in the frequency range from 10 Hz to 2 MHz and in the temperature range from 93 to 323 K. The composition dependence of the dc conductivity and the activation energy of these glasses has been compared with those of AgI-doped silver phosphate and borate glasses. The frequency-dependent electrical data have been analyzed in the framework of conductivity formalism. We have obtained the mobile ion concentration and the power-law exponent from the analysis of the conductivity spectra. We have observed that the concentration of Ag+ ions is independent of temperature and the conductivity is primarily determined by the mobility. A fraction of the Ag+ ions in the glass compositions are involved in the dynamic process. We have also shown that the power-law exponent is independent of temperature. The results are also supported by the temperature and composition independence of the scaling of the conductivity spectra.     

Conductivity and modulus formulation in lithium modified bismuth zinc borate glasses

The conductivity and modulus formulation in lithium modified bismuth zinc borate glasses with compositions xLi₂O–(50-x) Bi₂O₃–10ZnO–40B₂O₃ has been studied in the frequency range 0.1 Hz–1.5 × 10⁵ Hz in the temperature range 573 K–693 K. The temperature and frequency dependent conductivity is found to obey Jonscher's universal power law for all the studied compositions, the dc conductivity (σ_dc), crossover frequency (ω_H), and frequency exponent (s) have been estimated from the fitting of the experimental data of ac conductivity with Jonscher's universal power law. Enthalpy to dissociate the cation from its original site next to a charge compensating centre (H_f) and enthalpy of migration (H_m) have been estimated. It has been observed that number of charge carriers and ac conductivity in the lithium modified bismuth zinc borate glasses increases with increase in Li₂O content. Further, the conduction mechanism in the glass sample with x = 0 may be due to overlapping large polaron tunneling, whereas, conduction mechanism in other studied glass samples more or less follows diffusion controlled relaxation model. The ac conductivity is scaled using σ_dc and ω_H as the scaling parameter and is found that these are suitable scaling parameter for conductivity scaling. Non-Debye type relaxation is found prevalent in the studied glass system. Scaling of ac conductivity as well as electric modulus confirms the presence of different type of conduction mechanism in the glass samples with x = 0 and 5 from other studied samples. The activation energy of relaxation (E_R) and dc conductivity (E_dc) are almost equal, suggesting that polarons/ions have to overcome same barrier while relaxing and conducting.     

Electrical properties of LiBBaTe glass doped with Nd2O3

The dc and ac electrical conductivity of barium tellurite borate glass doped with Nd₂O₃ in the composition 50 B₂O₃- (20-X) BaO- 20TeO₂ 10 LiF or Li₂O where x = 0.5, 1, 1.5 and 2 Nd₂O₃ were measured in the temperature range 303–648 K and in the frequency range 0.1–100 kHz. The dc and ac conductivities values increase, whereas the activation energy of conductivities decreases with increasing Nd₂O₃ content in the glasses containing LiF and by the replacement of LiF by Li₂O the conductivity was found to decrease with addition of Nd₂O₃. The electrical conduction has been observed to be due to small polaron hopping at high temperatures. The frequency dependence of the ac conductivity follows the power law σ_AC (ω) = A ω^s. The frequency exponent (s) values (in the range 0.94 and 0.33) decreases with increasing temperature. The dielectric constant and dielectric loss increased with increasing temperature and decreased with increase in frequency for all glasses studied. In LiF glasses, it is observed that, the values of ?^\ and tan δ are observed to increase with the addition of Nd₂O₃ whereas they decrease in the glasses containing Li₂O. The electrical modulus formalism has been used for studying electrical relaxation behavior in studied glasses. It is for first time that the Nd₂O₃ doped barium tellurite borate glasses have been investigated for dc and ac conductivities and dielectric properties over a wide range of frequency and temperature.     

Dependence of the mixed alkali effect on temperature and total alkali oxide content in y[xLi2O·(1−x)Na2O]·(1−y)B2O3 glasses

The complex conductivity spectra of mixed alkali borate glasses of compositions y [xLi₂O·(1−x)Na₂O]·(1−y)B₂O₃ (with x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0; y=0.1, 0.2, 0.3) in a frequency range between 10⁻² Hz and 3 MHz and at temperatures ranging from 298 to 573 K have been studied. For each glass composition the conductivities show a transition from the dc values into a dispersive regime where the conductivity is found to increase continuously with frequency, tending towards a linear frequency dependence at sufficiently low temperatures. Mixed alkali effects (MAEs) in the dc conductivity and activation energy are identified and discussed. It has been for the first time found that the strength of the MAE in the logarithm of the dc conductivity linearly increases with the total alkali oxide content, y, and the reciprocal temperature, 1/T.     

Electric and dielectric properties of some gamma-irradiated cabal glasses

Electrical conductivity and dielectric properties have been studied for the glass system CaO---B₂O₃---Al₂O₃ in the temperature range 40–200°C. The substitution of 5% B₂O₃ by CaO or replacing 5% CaO by Na₂O or MgO cause a decrease in the conductivity, but the decrease obtained by soda is greater than that of magnesia. The activation energies of the tested glasses were calculated. All the glasses investigated showed a dielectric constant almost independent of temperature at fixed frequency. The effect of subjecting the glass to a constant dose of gamma-rays changes both the electrical conductivity and dielectric constant. The experimental results were discussed in relation to the specific conduction mechanism in such glasses. Also the effect of varying glass composition or temperature on the mobility or migration of current carrier was considered. The possible creation of induced defects in glass on irradiation was evaluated.     

Orientational and translational dynamics in room temperature ionic liquids

The authors investigate the dynamics of a series of room temperature ionic liquids, based on the same 1-butyl-3-methylimidazolium cation with different anions, by means of broadband (10(-6)-10(9) Hz) dielectric spectroscopy and depolarized light scattering in the temperature range from 400 K down to 35 K. Typical ionic conductivity is observed above the glass transition temperature Tg. Below Tg the authors detect relaxation processes that exhibit characteristics of secondary relaxations, as typically observed in molecular glasses. At high temperatures, the characteristic times of cation reorientation, deduced from the light scattering data, are approximately equal to the electric modulus relaxation times related to ionic conductivity. In the supercooled regime and close to Tg, the authors observe decoupling of conductivity from structural relaxation. Overall, room temperature ionic liquids exhibit typical glass transition dynamics, apparently unaltered by Coulomb interactions.     

"Cooperativity blockage" in the mixed alkali effect as revealed by molecular-dynamics simulations of alkali metasilicate glass

The relaxation dynamics of a complex interacting system can be drastically changed when mixing with another component having different dynamics. In this work, we elucidate the effect of the less mobile guest ions on the dynamics of the more mobile host ions in mixed alkali glasses by molecular-dynamics (MD) simulations. One MD simulation was carried out on lithium metasilicate glass with the guest ions created by freezing some randomly chosen lithium ions at their initial locations at 700 K. A remarkable slowing down of the dynamics of the majority mobile Li ions was observed both in the self-part of the density-density correlation function, Fs(k,t), and in the mean-squared displacements. On the other hand, there is no significant change in the structure. The motion of the Li ions in the unadulterated Li metasilicate glass is dynamically heterogeneous. In the present work, the fast and slow ions were divided into two groups. The number of fast ions, which shows faster dynamics (Levy flight) facilitated by cooperative jumps, decreases considerably when small amount of Li ions are frozen. Consequently there is a large overall reduction of the mobility of the Li ions. The result is also in accordance with the experimental finding in mixed alkali silicate glasses that the most dramatic reduction of ionic conductivity occurs in the dilute foreign alkali limit. Similar suppression of the cooperative jumps is observed in the MD simulation data of mixed alkali system, LiKSiO3. Naturally, the effect found here is appropriately described as "cooperativity blockage." Slowing down of the motion of Li ions also was observed when a small number of oxygen atoms chosen at random were frozen. The effect is smaller than the case of freezing some the Li ions, but it is not negligible. The cooperativity blockage is also implemented by confining the Li metasilicate glass inside two parallel walls formed by freezing Li ions in the same metasilicate glass. Molecular-dynamics simulations were performed on the dynamics of the Li ions in the confined glass. Slowing down of the dynamics is largest near the wall and decreases monotonically with distance away from the wall.     

Up-conversion luminescence analysis in ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses

Ytterbium-sensitized erbium-doped oxide-halide tellurite and germanate-niobic-lead glasses have been synthesized by conventional melting method. Intense green and red emissions centered at 525, 546 and 657 nm, corresponding to the transitions 2H11/2-->4I15/2, 4S3/2-->4I15/2 and 4F9/2-->4I15/2, respectively, were simultaneously observed at room temperature in these glasses. The quadratic dependence of the 525, 546 and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs. Tellurite glass showed a weaker up-conversion emission than germanate-niobic-lead glass, which is inconsistent with the prediction from the difference of maximum phonon energy between tellurite and germanate-niobic-lead glasses. In this paper, Raman spectroscopy was employed to investigate the origin of the difference in up-conversion luminescence in the two glasses. Compared with phonon side-band spectroscopy, Raman spectroscopy extracts more information including both phonon energy and phonon density. Our results reveal that the phonon density and the maximum phonon energy of host glasses are both important factors in determining the up-conversion efficiency.     

Effects of temperature and Cu-Doping on ionic conductivity of binary lithium borate glasses containing (BO3) triangles

Pure and several Cu₂O-doped binary lithium borate glasses have been prepared and annealed. Extensive measurements of the temperature-dependence of DC electrical conductivity were made on these samples and the corresponding activation energies of conduction were evaluated in each case. The results obtained are discussed in detail. They indicate that the phenomena of the formation of BO₃ triangles and a mixed alkali metal effect appear.     

Electrical conductivity studies in sulphate glasses and the mixed alkali effect

Electrical conductivities of alkali sulphate-zinc sulphate glasses have been measured. The variation of conductivity with compositon confirms the presence of the mixed alkali effect. The origin of mixed alkali effect has been explained on the basis of structural considerations reported earlier by us. Communication No. 160 from the Solid State and Structural Chemistry Unit.     

The spectroscopic properties of Er(3+)-doped TeO(2)-Nb(2)O(5) glasses with high mechanical strength performance

(100-x)TeO(2)-xNb(2)O(5) (x=5-20) niobic tellurite glasses doped with 0.5 mol.% Er(2)O(3) were synthesized, and their thermal, mechanical, and spectroscopic properties were measured and compared to the properties of the typical 75TeO(2)-20ZnO-5Na(2)O (TZN) tellurite glass. The refractive index (n(d)), density (rho), and glass transition temperature (T(g)) of bulk glasses increase with the Nb(2)O(5) content. The Vickers microhardness (H(v)) of bulk glass in niobic tellurite glasses also increases with the Nb(2)O(5) content. The values (2.5-3.2GPa) of H(v) in the niobic tellurite glasses are 47-88% larger than that (1.7GPa) in TZN glass. The effect of Nb(2)O(5) content on absorption spectra, the Judd-Ofelt parameters Omega(t) (t=2, 4, 6), fluorescence spectra and the lifetimes of Er(3+):I(13/2) level were also investigated, and the stimulated emission cross-section was calculated from McCumber theory. With increasing Nb(2)O(5) content in the glass composition, the Omega(t) (t=2, 4, 6) parameters, fluorescence full width at half maximum (FWHM) of I(13/2) of Er(3+) increase, while the (4)I(13/2) lifetimes of Er(3+) decreases. Compared with TZN glass, the gain bandwidth properties of Er(3+)-doped TeO(2)-Nb(2)O(5) glass is much larger than in tellurite glass based TeO(2)-ZnO-Na(2)O system, bismush-based glass, germanate, and silicate glasses, which indicates that TeO(2)-Nb(2)O(5) glasses are better choice as a practical available host material for broadband Er(3+)-doped amplifier.     

Thermal and electrical relaxation studies in Li(4+x)TixNb1−xP3O12 (0.0 ≤ x ≤ 1.0) phosphate glasses

A new superionic conducting transparent phosphate glasses with composition Li_(4+x)Ti_xNb_1?xP₃O₁₂ (0 ≤ x ≤ 1.0) were prepared by rapid melt quenching. As quenched samples were characterized by X-ray powder diffraction, differential scanning calorimetric and Fourier transform infrared spectroscopy studies. These glasses were found to have high thermal stability parameter and Li₄NbP₃O₁₂ has been found to have high glass forming ability. Electrical properties of the present glasses were studied by impedance and dielectric spectroscopy in the frequency range 10 Hz–3 MHz in the temperature range 323–523 K. Arrhenius behavior has been observed for all the glass in conductivity, dielectric loss and conductivity relaxation and their activation energies are explained and reported.     

Dielectric relaxation studies in transition metal ions doped tellurite glasses

Vanadotellurite and vanado-cobalt tellurite glasses were investigated for dielectric properties in the frequency range 50 Hz to 5 MHz and temperature range 300–500 K. Hunt's model has been invoked to analyze the data and the results indicated that the relaxation process has a local character and can be described by hops between each pair of sites. Activation energies for dielectric loss process were determined and they were in close agreement with dc activation energies. Barton, Nakijama and Namikawa's (BNN) linear relation between ac and dc conductivities has been verified in both the glass systems.