Electronic to ionic conductivity of glasses in the Li2S–Sb2S3–P2S5 system

There is great interest in sulfide glasses because of their high lithium ion conductivity. New sulfide glasses in the Li₂S–Sb₂S₃–P₂S₅ system have been synthesized by classical quenching technique. The glass domain relays on the medium-lithium content (up to 50% molar).Electrical conductivities of the samples have been determined by Impedance Spectroscopy. The isothermal conductivity curves exhibit two regions on dependence of lithium content implying that the conductivity mechanisms in these two regions are different. The compositions of low lithium content (below 20% mol.) have presented low electronic conductivities close to 10^− 8 S/cm at room temperature. The compositions of medium lithium content (30–50% mol.) could be mixed ionic–electronic conductors with predominant ionic conductivities with a maximum close to 10^− 6 S/cm for sample with 50% Li₂S at room temperature. Arrhenius exponential behavior is verified between 25 °C and T_g for all glasses. The activation energies, determined from temperature dependence, are 0.55–0.64 eV. A comparative study with glasses belonging to the other chalcogenide systems has been undertaken on base of the weak electrolyte model and the values of decoupling index, R_τ, are reported. The impedance of the 0.5Li₂S–0.3Sb₂S₃–0.2P₂S₅ ionic conductor can be described by an equivalent circuit R(RQ)(RQ).     

Conductivity relaxation in glass: Compositional contributions to non-exponentiality

That ionic conductivity in glass is a non-exponential process and has been known for many years. The amorphous structure of glass and hence a distribution of cation sites has often been thought to be the cause for the non-exponentiality. Almost completely unresearched, however, has been the effect of glass composition on the nature of the relaxation process. In this paper, we review the observations that have been made of the relationships between glass composition and the non-exponential character of the conductivity relaxation as well combine our recent wide composition range studies of sodium aluminoborate and lithium phosphate glasses to delineate the major features of the correlation. By examining glass compositions ranging from 0.02 to 60 mole% alkalioxide, it is observed that the rapid development of non-exponentiality within 1% Na₂O is accompanied by a similar rapid decrease in the average cation-cation separation distance, this being calculated using the composition and density. Other quantities such as the dc conductivity or activation energy are observed to vary too slowly with composition to produce a linear correlation with the extent of non-exponentiality as monitored in the parameter of the stretched exponentialkww function.     

Ionic conduction and dielectric relaxation in Ag/Na ion-exchanged aluminosilicate glasses: mixed mobile ion effect and KWW relaxation

Ag⁺/Na⁺ ion-exchanged aluminosilicate glasses with uniform concentration profiles were prepared, and their electrical conductivities were investigated as functions of the ion-exchange ratio and the initial glass compositions. In the case of the ion-exchanged glasses of x20Ag₂O–(1−x)20Na₂O–10Al₂O₃–70SiO₂ in mol%, the conductivity, σ, and its activation energy, E_σ, showed a minimum and a maximum at the same ion-exchange ratio x=0.3, respectively, and the mixed mobile ion effect (MMIE) was observed. The fully ion-exchanged sample attained σ=3.5×10⁻⁵ S/cm at 200 °C, which was 1.5 orders of magnitude larger than that of initial glass. In the case of x25Ag₂O–(1−x)25Na₂O–25Al₂O₃–50SiO₂, the mixed mobile ion effect was also observed at x=0.5. The maximum conductivity of 2×10⁻⁴ S/cm at 200 °C was obtained in the fully ion-exchanged glass sample.

The electric relaxation analysis was also conducted on both systems, and Kohlrausch–Williams–Watts (KWW) fractional exponent β was obtained as a function of x. The decrease of β was observed near x≈0.3 in the former system, while that of the later system was independent of the ion-exchange ratio. Based on the structural analysis results, the observed behaviors were investigated from the point of view of the occupation of Ag⁺ ions on the non-bridging oxygen-site (NBO-site) and the charge compensation-site (CC-site) of AlO₄ tetrahedral unit.     

Fast Na+ ion conductivity in glass,intermediate and crystalline phases of Na4UO2(SO4)3

The ac electrical conductivity, DSC calorimetry and density data for pure Na₄UO₂(SO₄)₃ and for compound incorporating guest ions Rb⁺, Cd²⁺, Gd³⁺, SiO ₄ ^4– in the glass, quasi-crystalline intermediate and crystalline phases are reported. The glass phase conductivity data show an increase in Na⁺ conductivity by a factor 10³ relative to pure crystalline Na₂SO₄ in the low temperature (LT) region, i.e. 180°C. There is no onset of phase transition up to 260°C. The distinct conductivity regimes prior to devitrification in the glass suggest that higher energy or excited structural states/configurations can exist in the glass phase. The apparent activation energy Q _c value 76±5 kJ/mole for the glass state of all compositions is in excellent agreement with the Na₂SO₄ III Q _c value. The conductivity regime immediately after devitrification with Q _c of 40±3 kJ/mole represents the stable intermediate phase. The conductivity of the final product of devitrification on cooling resembles crystalline behavior except for (Na_3.5Rb_0.5)UO₂(SO₄)₃. A gradual jump in conductivity accompanies the transition in the crystalline sample. The Q _c value is 75±5 kJ/mole for the (HT) phase conductivity in the heating mode but remains constant at 66±5 kJ/mole for the (LT) phase in the heating mode and for both and phases in the cooling mode.The excellent conductivity-volume, i.e. /V correlation is consistent with the free volume contribution to conductivity enhancement and the percolation-type mechanism of transport.This study received partial support from the Natural Sciences and Engineering Research Council of Canada     

Enhanced ionic conductivity in La3+ and Sr2+ co-doped ceria: carbonate nanocomposite

Ionics - A series of ceria-based nanocomposites consisting of Ce0.85La0.125Sr0.025O1.9125 (LSCO) and binary carbonate mixture Li2CO3–Na2CO3 (LNCO) have been prepared as functional...     

An anomalous enhancement in the electrical conductivity of Li2O : B2O3 : Al2O3 glasses

The study of electrical conductivity of 27.5 Li₂O : (72.5 − x) B₂O₃ : x Al₂O₃ glass samples has been carried out. It has been observed that the conductivity exhibits Arrhenius behavior for all samples up to glass transition temperature T_g. Beyond T_g, an anomalous enhancement followed by decrease in conductivity has been observed. The results have been explained by dividing the temperature range into two regions. In region-I, it has been observed that the conductivity variation exhibits a maximum at 2.5 mol% Al₂O₃, which has been explained on the basis of Mixed Glass Former Effect (MGFE). An anomalous enhancement in the conductivity observed in region-II has been attributed to the nucleation in the glass. The subsequent decrease in the conductivity has been attributed to the crystallization of the glass samples.     

Electrical conductivity relaxation in PVOH+LiH2PO4+Al2O3 polymer composites

Low-frequency conductivity measurements have been performed in solid polymer electrolyte composites based on the anhydrous PVOH–LiH₂PO₄–Al₂O₃ system. A typical power law dependency in the real part of the conductivity, at higher frequencies, of the form ω ⁿ is observed, with an exponent n that depends on the alumina content and nearly independent of temperature. An analysis of the frequency dependence of the electrical susceptibility is conducted to obtain relaxation functions of the form exp[?(t/τ) ^β ], with an exponent β?≈?n???1. Correlation times, τ, and parameters characterizing the electrical relaxation in time and frequency domains are compared to show the equivalence of these representations. The anhydrous dc conductivity of the electrolytes increases with increasing lithium salt content, becoming of the order of 10^?5 S/cm for a salt molar fraction of x?=?0.14. This conductivity value increased by about one order of magnitude by addition of nanoporous particles of Al₂O₃. The temperature dependence of the samples conductivity was well described by the Vogel–Tammann–Fulcher’s equation indicating the effect of the polymer chains flexibility on ion migration. Although all membranes exhibited a “universal dynamic response” associated to the random hopping of the mobile carriers, variations in the measured relaxation parameters with alumina content indicate an increase of ionic correlations when adding the nonporous particles to the polyelectrolyte.     

Scaling of the conductivity spectra in ionic glasses: dependence on the structure

A scaling approach in the conductivity formalism is applied to lithium tellurite glasses of different compositions. We observe that the hopping frequency can be used as the scaling frequency in the absence of well-defined dielectric loss peaks, and a universality of the scaling of the conductivity can be obtained for compositions with a similar structure. Further, the reasons behind the inapplicability of the scaling approach reported recently are elucidated in terms of structure of the glasses.     

Gamma-ray induced reduction of W6+ into W5+ in the Na2O -WO3 glasses

The ESR spectra of the 38Na₂O · 62WO₃ glasses irradiated with the⁶⁰Co -rays of 10⁵–10⁶ Gy comprised a broad singlet peak (g=1.65, H _pp=28.6 mT), a narrow singlet (g=2.00₁, H _pp=1.36 mT), and a narrow doublet (g=2.00₁, H _pp=0.72 mT,A=4.96 mT). The broad singlet and the two narrow peaks were respectively ascribed to the W⁵⁺ and the W-OHC (oxygen hole center) produced by the -ray irradiation. The _D (360 K) and _E (180 K), obtained from the low-temperature¹¹⁹Sn-Mössbauer measurement of 38Na₂O · 61WO₃·SnO₂ glass, indicated that octahedral Sn⁴⁺ substituted for octahedral W⁶⁺ and played a role of network former (NWF). A gradual increase in the isomer shift () from –0.02 to 0.09 mm s^–1 was observed with an increasing -ray dose, due to the charge transfer from oxygen to the Sn⁴⁺.     

Low-dimensional spin S = 1/2 system at the quantum critical limit: Na2V3O7

We report the results of measurements of the dc susceptibility and the 23Na-NMR response of Na2V3O7, a recently synthesized, nonmetallic low dimensional spin system. Our results indicate that, upon reducing the temperature to below 100 K, the V4+ moments are gradually quenched, leaving only one moment out of nine active. The NMR data reveal a phase transition at very low temperatures. With decreasing applied field H, the critical temperature shifts towards T=0 K, suggesting that Na2V3O7 may be regarded as an insulator reaching a quantum critical point at H=0.     

Glass formation and structure of glasses in the Na2O-PbO-SiO2-SO3 system

Translated from Zhurnal Prikladnoi Spketroskopii, Vol. 51, No. 2, pp. 267–272, August, 1989.     

Skin effect in metals: Passage to the infinite conductivity limit

The infinite conductivity limit in the classical skin effect in metals is considered. The analysis is carried out with and without taking into account the influence of free electron relaxation, as well as local relationships between the electric field and current density, in the free electron model. Both ultimately nonlocal and real limits are considered for the indefinitely increasing free path.     

Cathodoluminescence of Eu2+ in EuGa2S4 and Ga2S3:Eu2O3

We present the results of an investigation of the cathodoluminescence of the Eu²⁺ ion in gallium chalcogenides (Ga₂S₃) and europium thiogallate (EuGa₂S₄). We show that the intense wide-band radiation of these compounds is due to the 4f-5d transitions of the Eu²⁺ ions. With increase in the Eu²⁺ percent composition from 0.1 to 5.0 mol.% the luminescence brightness increases and then decreases. Translated from Zhurnal Prikladnoi Spektrskopii, Vol. 67, No. 2, pp. 268–270, March–April, 2000.     

Fast excited-state relaxation of Eu-Eu pairs in commercial Y2O3: Eu3+ phosphors

Low-temperature, dye-laser excitation spectroscopy of commercial Y₂O₃:Eu³⁺ phosphors reveals the presence of complex structure in the excitation lines of the ⁵D₀ and ⁵D₁ manifolds. The structure is associated with the presence of Eu³⁺ ion pairs. The kinetics of the emission decay are observed to be drastically different when excitation occurs either at the center or on the wings of the excitation lines, suggesting faster inter-level and/or inter-site energy transfer on exciting into the line wings. Low-temperature vibronic spectra are reported for the ⁷F₀→⁵D₀ transitions for both C₂ and C_3i sites. Evidence is presented for the detection of the highly forbidden ⁷F₀→⁵D₀ transition for the C_3i site.     

Codoping Na+ to modulate the spectroscopy and photoluminescence properties of Yb3+ in CaF2 laser crystal

Three kinds of Yb3+ - and Na+-codoped CaF2 laser crystal with different Na:Yb ratios of 0, 1.5, and 10 are grown by the temperature gradient technique. Room-temperature absorption, photoluminescence spectra, and fluorescence lifetimes belonging to the transitions between ground state 2F7/2 and excited state 2F5/2 of Yb3+ ions in the three crystals are measured to study the effect of Na+. Experimental results show that codoping Na+ ions in different Na:Yb ratios can modulate the spectroscopy and photoluminescence properties of Yb3+ ions in a CaF2 lattice in a large scope.     

The fine structure levels and spin-singlet contributions to zero-field-splitting parameters of Cr2+ ion in CdGa2S4

A theoretical investigation is reported of the fine structure levels and the spin-singlet contributions to zero-field-splitting (ZFS) parameters for Cr²⁺ ion in CdGa₂S₄ crystals. Firstly, the complete energy matrix including all spin states for a 3d ⁴ ion in tetrahedral D _2d symmetry is constructed according the double-group chain in the strong-field scheme. Then, by diagonalizing the complete energy of electron–electron interactions, the crystal field and the spin–orbit coupling for the Cr²⁺ (3d ⁴) ion in CdGa₂S₄ crystal, the fine structure levels and the spin-singlet contributions to ZFS parameters a, D and F are calculated. The results show that the spin-singlet contribution to D is negligible, but the contributions to a and F are very important. So, to obtain more accurate ZFS parameters for 3d ⁴ ions in the tetrahedral crystals, all spin states should be considered.     

Electric conductivity and relaxation in ZnF2–AlF3–PbF2–LiF glasses

The electric conductivity of ZnF₂–AlF₃–PbF₂–LiF glasses has been studied in the frequency range 10 Hz–2 MHz and in the temperature range from 300 K to just below the glass transition temperature. The conductivity decreases with the increase in the LiF content in the composition, which results from the trapping of F⁻ ions by Li⁺ ions. Small values of the stretching exponent β are observed for the present glasses. The value of the decoupling index decreases with an increase in LiF content, consistent with the composition dependence of the conductivity.