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.     

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.     

Electrical conductivity and relaxation in mixed alkali tellurite glasses

The authors have reported the electrical conductivity and the conductivity relaxation in mixed alkali tellurite glasses of compositions of 70TeO2-xNa2O-(30-x)Li2O 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. They have analyzed the relaxation data in the framework of different models. They have observed the mixed alkali effect in the dc and ac conductivities, the crossover frequency, and the conductivity relaxation frequency as well as in their respective activation energies in these glasses. They have also observed the mixed alkali effect in the decoupling index. The scaling property of the modulus spectra of these mixed alkali glasses shows that the conductivity relaxation in the mixed alkali tellurite glasses is independent of temperature but depends on the glass compositions.     

Optical and ESR studies of silver clusters

The optical and ESR spectra of Ag(O), Ag₂⁺ and Ag₄³⁺ centres formed in γ-irradiated aqueous and ethanol glasses have been monitored under identical conditions. The ESR spectra of the Ag(O) centres sugest that they initially retain the solvation of the parent Ag⁺ ions but that solvent molecules are gradually lost on annealing. This loss is reflected in marked high-frequency shifts in the electronic transitions. An intense band observed in the range 265–290 nm grew in simultaneously. This is assigned to Ag₂³⁺ ions. These have a well characterised ESR spectrum, but have not previously been studied optically.     

Electrical relaxation of bismuth germanate silicate glasses

The frequency-dependent electrical data of the bismuth germanate silicate (BGSO) glasses have been discussed in the framework of the electric modulus representation and the power-law conductivity. The activation energies of the mean electric relaxation time and the direct current (dc) conductivity obtained by the complex modulus analysis show that the BGSO glasses satisfy the Barton, Nakajima, and Namikawa (BNN) relation. The proper relation between the exponent of the power-law conductivity and the stretched exponential of the modulus representation is shown. The temperature- and frequency-dependent characteristics of non-Debye behavior are discussed. The scaling properties of both the modulus M*(omega) and the alternating current (ac) conductivity sigma(omega) are examined.     

EPR and optical investigations of manganese ions in alkali lead tetraborate glasses

Electron paramagnetic resonance (EPR) and optical absorption spectra of Mn2+ ions in different alkali lead tetraborate glasses 90R2B4O7+9.25PbO+0.75MnSO4 (R=Li, Na and K) and 90Li2B4O7+(10-x)PbO+xMnSO4 (x=0.1, 0.25, 0.5, 0.75, 1.0, 1.25, 1.5 and 2 mol%) have been studied. The EPR spectrum of all the glass samples exhibit three resonance signals at g=2.0, 3.3 and 4.3. The resonance signal at g=2.0 is attributed to the Mn2+ ions in an environment close to an octahedral symmetry. The resonance signals at g=3.3 and 4.3 have been attributed to the rhombic symmetry of the Mn2+ ions. The effect of temperature (123-433 K) and the composition dependence of EPR signals have been studied for Mn2+ ions in lithium lead tetraborate glasses. It is interesting to observe that the variation of paramagnetic susceptibility (chi) with temperature obeys Curie-Weiss law. From the slope of 1/chi versus T graph, the Curie constant (C) has been evaluated. The zero-field splitting (zfs) parameter D has been calculated for different alkali lead tetraborate glasses from the intensities of the allowed hyperfine lines. The optical absorption spectrum exhibits three bands. An intense and broad band at lower energy side has been assigned to the spin-allowed (5Eg-->5T2g) transition of Mn3+ ions in an octahedral symmetry. The intense and sharp band and a broad band at higher energy side have been assigned to charge transfer bands. A red shift is observed with increase of alkali ion size. The optical band gap energy (Eopt) decreases, whereas the Urbach energies (DeltaE) increases with increase of Mn content. The theoretical values of optical basicity (Lambdath) of the glasses have also been evaluated.     

Effect of Bi2O3 addition on electron paramagnetic resonance, optical absorption, and conductivity in vanadyl-doped Li2O-K2O-Bi2O3-B2O3 glasses

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.     

Hopping rates and concentrations of mobile fluoride ions in Pb(1-x)Sn(x)F(2) solid solutions

In the present paper, the ion dynamics and relaxation of fluoride ions in Pb(1-x)Sn(x)F(2) (with x=0.2-0.6) solid solutions, prepared by mechanochemical milling, are studied in the conductivity formalism over wide ranges of frequencies and temperatures. The conductivity spectra of the investigated materials are analyzed by the Almond-West (AW) power-law model. The estimated values of the hopping rates and the dc conductivity of different compositions are thermally activated with almost the same activation energy. The calculated values of the concentration of mobile ions, n(c), are almost independent of temperature and composition for x=0.2-0.4. The maximum value of n(c) is obtained for the x=0.6 sample, although it does not show the maximum conductivity. Therefore, the composition dependence of the ionic conductivity of these solid solutions could be explained based on the extracted parameters. The results presented in the current work indicate that the AW model represents a reasonable approximation of the overall frequency-dependent conductivity behavior of the investigated materials. The conductivity spectra at different temperatures for each composition are successfully scaled to a single master curve, indicating a temperature-independent relaxation mechanism. For different compositions, however, the conductivity spectra cannot be scaled properly, indicating composition-dependent relaxation dynamics.     

Thermal and optical properties of Tm3+ doped tellurite glasses

Ultraviolet, visible (UV/VIS) and differential thermal analysis (DTA) measurements were carried out in order to investigate the optical and thermal properties of various 0.5 mol.% Tm2O3 containing (1 - x)TeO2 + xLiCl glasses in molar ratio. The samples were prepared by fusing the mixture of their respective reagent grade powders in a platinum cricuble at 750 degrees C for 30 min. DTA curves taken in the 23-600 degrees C temperature range with a heating rate of 10 degrees C/min reveal a change in the value of the glass transition temperature, Tg, while melting was not observed for the glasses containing LiCl content less than 50 mol.%. These glasses were found to be moisture-resistant. However, the glasses with LiCl content higher than 50 mol.%, in which a melting peak was observed at Tc = 401 degrees C, were moisture-sensitive. Absorption measurements in the UV/VIS region of the glasses without Tm2O3 content show that the Urbach cutoff occurs at about 320 nm and, is relatively independent of the LiCl content. Six absorption bands were observed in the Tm2O3 doped glasses corresponding to the absorption of the 1G4, 3F2, 3F3 and 3F4, 3H5 and 3H4 levels from the 3H6 ground level of Tm3+ ions. The spectra also show that the integrated absorption cross-section of each band depends on the glass composition. Judd-Ofelt theory was used to determine the Judd-Ofelt parameters as well as the radiative transition probabilities for the metastable levels of Tm3+ ions in (0.3)LiCl + (0.7) TeO2: 0.01 Tm2O3 glass which is moisture-resistant.     

Thermal,structural and electrical studies of bismuth zinc borate glasses

Bismuth Zinc Borate glasses with compositions xBi₂O₃–30ZnO–(70 − x)B₂O₃ (where x = 30, 35, 40 and 45 mol %) have been prepared by melt quenching method. These glasses were characterized by X-ray diffraction (XRD), Differential Thermal Analysis (DTA), Fourier Transform Infrared Spectrometer (FTIR) and Broad Band Dielectric Spectrometer (BDS). DTA and FTIR analysis reveals that Non-Bridging Oxygens (NBOs) increase with increase of bismuth content in the glass. Electrical data have been analyzed in the framework of impedance and modulus formalisms. The activation energy for dc conductivity decreases with increase of bismuth concentration. The imaginary part of modulus spectra has been fitted to non-exponential Kohlrausch–Williams–Watts (KWW) function and the value of the stretched exponent (β) is found to be almost independent of temperature but slightly dependent on composition.     

VO2+ ions in zinc lead borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of vanadyl ions in zinc lead borate (ZnO-PbO-B2O3) glass system have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of VO2+ ions. The values of spin-Hamiltonian parameters indicate that the VO2+ ions in zinc lead borate glasses were present in octahedral sites with tetragonal compression and belong to C4V symmetry. The spin-Hamiltonian parameters g and A are found to be independent of V2O5 content and temperature but changing with ZnO content. The decrease in Deltag( parallel)/Deltag( perpendicular) value with increase in ZnO content indicates that the symmetry around VO2+ ions is more octahedral. The decrease in intensity of EPR signal above 10 mol% of V2O5 is attributed to a fall in the ratio of the number of V4+ ions (N4) to the number of V5+ ions (N5). The number of spins (N) participating in resonance was calculated as a function of temperature for VO2+ doped zinc lead borate glass sample and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility was calculated at various temperatures and the Curie constant was evaluated from the 1/chi-T graph. The optical absorption spectra show single absorption band due to VO2+ ions in tetragonally distorted octahedral sites.     

Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3-ZnO-PbO glasses

This paper reports on the spectral properties of Mn2+, Co2+ and Ni2+ ions doped B2O3-ZnO-PbO glasses. XRD, FT-IR spectra and DSC profiles of these glasses have also been carried out, and the FT-IR profiles have shown the presence of both BO3 and BO4 units. It is interesting to notice that the FT-IR peak positions are slightly shifted towards higher energy with an increase in transition metal ion concentration change. From the measured DSC thermograms, glass transition (T(g)), crystallization (T(c)) and temperature of melting (T(m)) have been evaluated. From the UV absorption spectra of Mn2+, Co2+ and Ni2+ ions doped glasses, both direct and indirect optical band gaps have been calculated. The visible absorption spectra of Mn2+:glasses have shown a broad absorption band at 520 nm (6A1g(S) --> 4T1g(G)); with Co2+ ions one absorption band at 605 nm (4A2(4F) --> 4T1(4P)) and another at 1450 nm (4A2(4F) --> 4T1(4F)); and for Ni2+:glasses three absorption bands at 420 nm (3A2g(F) --> 3T1g(P)), 805 nm (3A2g(F) --> 1Eg(D)) and 880 nm (3A2g(F) --> 3T1g(F)) have been observed. For Mn2+:glasses, upon excitation with 262 nm, a green emission (539 nm) with a slight blue shift; and with 392 nm, a green emission (534 nm) with a slight red shift with Mn2+ ions concentration change (0.2-0.5 mol%) has been observed. This green emission has been assigned to (4T1(G) --> 6A1(S)) d-d transition of Mn2+ ions that are in tetrahedral co-ordination. For 0.5 mol% Co2+ ions doped glass, upon excitation with 580 nm, a red emission (625 nm) has been observed which originates from 2E(2G) --> 4A2(4F) transition of Co2+ ions in tetrahedral co-ordination. For Ni2+ ions doped glasses upon excitation with 420 nm, a green (577 nm) and red (670 nm) emissions are observed and are assigned to (1T2g(D) --> 3A2g(F)) and (1T2g(D) --> 3T2g(F)) d-d transitions of Ni2+ ions in octahedral co-ordination.     

AC conductivity studies and relaxation behaviour in (LiX) y [(Li2O)0.6(P2O5)0.4](1 − y) glasses

The electrical conductivity of (LiX) _y [(Li₂O)_0.6(P₂O₅)_0.4]_(1???y) (X?=?Cl, Br, y?=?0, 0.1, 0.15, 0.2) glasses has been determined over a wide range of temperature and frequency by means of impedance spectroscopy. The real part of the frequency-dependent conductivity exhibits a simple power law feature, and the dimensionless frequency exponent n has been determined. The conductivity spectra show scaling behaviour when the conductivity spectra are scaled by ω/(σ _dc T) and ω/ω _p . The conductivity relaxation time and activation energy have been estimated from the modulus spectra. Increases of ionic conductivity values with addition of LiX content are in line with the decrease of activation energy and relaxation time.     

Ionic conductivity of superionic conducting glasses in the pseudobinary system AgIAg2MoO4

The ionic conductivity was measured in the temperature range 250–300 K as a function of composition of superionic conducting glasses in the pseudobinary system AgIAg₂MoO₄. The conductivity, ranging from 10^?2 to 10^?4 Ω^?1 cm^?1 at room temperature, increases linearly in logarithmic scale with increasing AgI content, while the total silver ion concentration remains nearly constant in the whole glass-forming region of the present system. Such a composition dependence of conductivity is considered to be evidence that only a fraction of the silver ions in glass contributes to the ionic conduction. The conductivity and the activation energy for conduction differ slightly between bulk glasses and pressed pellets of pulverized glasses. The close agreement in bulk glasses and pellets suggests that bulk rather than grain boundary or surface diffusion dominates the conduction process in the present glasses.     

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.     

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.     

Color Centers in Alkali Borate Glasses Containing Cobalt,Nickel, or Copper

The absorption spectra and the magnetic moments of Co²⁺, Ni²⁺, and Cu²⁺ in alkali borate glasses of various compositions and in halide-containing glasses have been explained from the point of view of the ligand field theory. Spectra and magnetic moments are highly dependent on the composition of the base glass; this must be ascribed to the change in the coordination of the transition-metal ions. There are far-reaching analogies with corresponding complexes in solution or in the crystalline state.     

层状钴氧化物Bi2-xAgxSr2Co2O8-δ的高温热电性能及XPS研究

采用固相反应法制备了组成为Bi_2-xAg_xSr₂Co₂O_8-δ(x=0.0, 0.4, 0.8,略写为BAC-222)的层状钴氧化物陶瓷。利用X-射线光电子能谱考察该类化合物的电子结构,结果表明钴离子以Co³⁺和Co⁴⁺混合价态形式存在,n_Co⁴⁺/n_Co³⁺的比例随着Ag掺杂的量增加而增加。O1s光电子谱显示在所有样品中均存在点阵氧和吸附氧。热电性能测试结果显示,随着Ag掺杂量的增加,电导率显著增加而Seebeck系数几乎保持不变,Ag的引入极大的影响了BAC-222的电子输运性质,其功率因子在1 123 K时达到了1.23×10^-4 W·m^-1·K^-2,是一种具有很好应用前景的热电材料。