Electrical conductivity studies in single and mixed alkali doped cobalt-borate glasses

The glasses of the type (Li₂O)_x-(CoO)_0.2-(B₂O₃)_0.8−x and (Li₂O)_0.2-(K₂O)_x-(CoO)_0.2-(B₂O₃)_0.6−x were prepared by melt quench technique and their non-crystallinity has been established by XRD studies. The glasses were investigated for room temperature density and dc electrical conductivity in the temperature range 300-550 K. Molar volumes were estimated from density data. Composition dependence of density and molar volume in both the sets of glasses has been discussed. Conductivity data has been analyzed in the light of Mott’s Small Polaron Hopping (SPH) Model and activation energies were determined. Variation of conductivity and activation energy with Li₂O content in single alkali glasses indicated change over conduction mechanism from predominantly electronic to ionic, at 0.4 mole fraction of Li₂O. In mixed alkali glasses, the conductivity has passed through minimum and activation energy has passed through maximum at x = 0.2. This has been attributed to the mixed alkali effect. It is for the first time that a change over of predominant conduction mechanism in lithium-cobalt-borate glasses and mixed alkali effect in lithium-potassium-cobalt-borate glasses has been observed. Various physical and polaron hopping parameters such as polaron hopping distance, polaron radius, polaron binding energy, polaron band width, polaron coupling constant, effective dielectric constant, density of states at Fermi level have been determined and discussed.     

Multichannel conduction in alkali silicate glasses

The qualitative change of the electrical conduction of alkali silicate glasses with alkali mixing is discussed in connection with dielectric and mechanical relaxation. The observed conduction is understood as the additive effect of two kinds of independent diffusion processes — I and II. In single alkali glass, diffusion process-I is always observed as the dominant conduction process. However, when one alkali is progressively substituted by another, the dominant conduction process is altered from diffusion process-I to II. In the mixed alkali glass containing equal amounts of two alkali ions, diffusion process-I disappears, so that only diffusion process-II is observed. Consequently, it becomes evident that the mixed alkali effect is not only the successive change of conductivity, but the alternation of the dominant conduction process.     

Relaxation in mixed alkali fluoride glasses

We have investigated the dynamics of alkali cations as well as fluorine anions in non-oxide fluoride glasses with a total alkali fluoride content varying from 16 to 35 mol% 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 shown that the dc and ac conductivity, crossover frequency and conductivity relaxation frequency exhibit a minimum in mixed alkali fluoride glasses, where anions also participate in the diffusion processes in addition to cations, unlike mixed alkali oxide glasses and crystals. We have observed lower dimensionality of the conduction pathways in mixed alkali fluoride glasses compared to that in the single alkali glasses. We have shown that the relaxation dynamics in mixed alkali fluoride glasses is independent of temperature.     

Structure and properties of lanthanum galliogermanate glasses

Lanthanum galliogermanate glasses were prepared. Raman spectra, molar volumes, glass transition temperatures and activation energies for glass transition and crystallization were obtained. For glasses having the same La₂O₃/GeO₂ ratio, the molar volumes increase with the Ga₂O₃ content, and the glass transition temperatures, activation energies for glass transition and crystallization, increase initially then decrease as the ratio of Ga₂O₃/GeO₂ increases. For glasses having the same Ga₂O₃/GeO₂ ratio, the molar volumes increase with La₂O₃ content, and the glass transition temperatures increase as the ratio of La₂O₃/GeO₂ increases. The change of glass structure and its properties with composition is correlated with the concentration of lanthanum ion.     

The mixed alkali effect in lithium-sodium borate glasses

The electrical conductivity of a series of 0.35 (Li, Na)₂O·B₂O₃ glasses shows a minimum at the composition Na/(Na+Li)～0.6, which becomes stronger as the temperature is decreased; the activation enthalpy for electrical conductivity shows a maximum at this composition. In general, replacing 1% of the total oxygen concentration by chlorine or bromine (keeping the total alkali content fixed) in these glasses increases the conductivity; fluorine doping has an opposite effect. The mixed alkali effect, expressed in terms of the compositional dependence of the activation enthalpy for conductivity, is enhanced when borate glass is doped with fluorine, but is slightly diminished when doped with chlorine or bromine. The results are explained in terms of the structure of halogenated alkali-borate glasses, and discussed in relation to the origin of the mixed alkali effect.     

Activation volumes and site relaxation in mixed alkali glasses

Evidence is presented for site relaxations occurring in mixed alkali (cation) glasses based on activation volumes, V_A(σ) = −RT[d ln σ/dp]_T, which are determined for sodium aluminoborate glasses of varying Na₂O content, and for mixed alkali glasses where Na⁺ is partially replaced by Li⁺, K⁺ or Cs⁺ ions. In accordance with the ‘updated’ dynamic structure model, activation volumes are identified here with local expansions that accompany the opening up of C′ sites to admit incoming ions. ‘Anomalous’ increases in activation volume in mixed cation glasses correlate with the size of minority (guest) cations. This anomaly is interpreted in terms of a ‘leader follower’ mechanism that involves dynamic coupling between the faster (majority) and slower (minority) cations. Because of mismatch effects in mixed cation glasses this coupling requires the opening up of additional cation sites by the slower follower cations. The resulting disturbances in the glass network are responsible for many characteristic features of the mixed alkali effect, including the appearance of high temperature internal friction peaks and observed minima in glass transition temperatures and melt viscosities.     

The mixed alkali effect in the Na2OCs2OSiO2 glasses

As an approach to the mixed alkali effect in glass, the self-diffusion coefficients of sodium and cesium ions in Na₂OCs₂OSiO₂ glasses were measured at temperatures 350–550°C. Electrical conductivity of the glasses and the transport number for sodium ions were also measured. The substitution of the alkali ions in the glass by different alkali ions caused the mobility of each alkali ion to decrease pronouncedly and the activation energy for migration to increase rapidly. The increase of activation energy was attributed to an increase in alkali-oxygen bond strength resulting from the presence of two kinds of alkali ions. This is related to the expectation that the activity of the alkali ions decreases when two alkali ions are mixed.     

Relaxation processes in mixed alkali NaK methaphosphate glasses

The internal friction and the dielectric losses of NaK metaphosphate glasses have been investigated. A single alkali and a mixed alkali internal friction peak were observed. The single alkali peak shifted to higher temperatures with increasing concentration of the second alkali and eventually disappeared. The activation energy of this peak increased with the alkali mixing ratio. As in silicate and borate glasses, the single alkali peak correlates closely with the dielectric loss. The mixed peak showed a dramatic increase in size with the addition of the second alkali, but the activation energy was practically independent of the alkali mixing ratio. The large reduction in height of the mixed peak, observed on annealing, is discussed together with the influence of water.     

Electrical properties of copper phosphate glasses I. DC electrical behaviour

The ac and dc electrical properties of the P₂O₅BaOCuO glass system have been measured.TSPC and TSDC experiments and dc conductivity as a function of time indicate the predominantly electronic character of these glasses. The conduction process can be basically explained by a polaron hopping model in an adiabatic regime. Conductivity values which depend on the glass microstructure and switching phenomena are observed. The filamentary-feature of this process suggests a Poole-Frenkel mechanism.A Debye dielectric relaxation non-simple process is deduced from the frequency and temperature dependence of loss tangent and dielectric constant. The activation energies agree with those determined from dc measurements, suggesting a unique electronic hopping conduction mechanism in both regimes.The ac and dc electrical properties are strongly affected by the glass composition and essentially by the redox Cu⁺/Cu_t ratio.A conduction model accounting for ac and dc behaviour is finally proposed.     

Synthesis and characterization of potassium, rubidium, and cesium thiogermanate glasses

Glass-forming regions were investigated for the binary xM₂S + (1 − x)GeS₂ (M=K, Rb, Cs) systems. Glasses were prepared from 0?x?0.20 mole fraction alkali sulfide using a novel preparation route involving the decomposition of the alkali hydrosulfides in situ. At higher alkali concentrations near x=0.33, the glass-forming regions are limited by the readily formed adamantane-like M₄Ge₄S₁₀ crystals. Structural characterization of the glasses and polycrystals for x?0.33 were performed using Raman scattering and IR absorption. Terminal Ge-S⁻ vibrational modes, observed between 473 and 479 cm⁻¹, increased in intensity and decreased in frequency with increasing alkali modifier content. Glass transition temperatures decreased with increasing alkali modifier, ranging from 250 to 215 °C. Corresponding crystallization onset temperatures were between 340 and 385 °C. DC conductivity values of the glasses ranged from 10⁻¹⁰ to 10⁻⁷ (Ω cm)⁻¹ with activation energies between 0.54 and 0.93 eV for the temperature range of ∼100-250 °C. Higher ionic conductivities were observed with increasing alkali concentration and decreasing alkali radii. Additionally, an increase in the activation energy was observed above the glass transition temperature.     

Alkali diffusion and electrical conductivity in sodium borate glasses

The diffusion coefficient of sodium, ²²Na, and silver, ¹¹⁰Ag, and electrical conductivity for sodium borate glasses (4–24 mol% Na₂O) has been measured from 100°C to slightly below the glass transition temperature, T_g. Unlike silicate glasses where the self-diffusion coefficient is much larger than the impurity diffusion coefficient, D_Na and D_Ag had close to the same magnitude in the sodium borate glasses. In some glasses, D_Ag was slightly larger than D_Na. Na₂O-Ag₂O-B₂O₃ glasses show a relatively small mixed alkali effect, despite the significant mass difference between Ag(≈108) and Na(≈23). It is concluded that the mixed alkali effect is more dependent upon the difference in ionic radii rather than differences in mass.     

Synthesis and characterization of SnO-containing phosphorous oxynitride glasses

SnO-containing oxynitride phosphate glasses have been obtained by ammonolysis and their structure studied by nuclear magnetic resonance. The nitrided glasses are characterized by tetrahedral units P(O,N)₄ in which nitrogen atoms have substituted both bridging and non-bridging oxygen atoms. The N/O substitution in the anionic network induces important changes in the glass properties such as an increase in the glass transition temperature and a decrease in the coefficient of thermal expansion. ³¹P MAS NMR shows that PO₄, PO₃N and PO₂N₂ units coexist within the vitreous network and their relative proportions are a function of the nitrogen content as well as of the base glass composition. The influence of the different modifiers on the nitridation process is explained through a comparative study of the LiNaSnPON and LiNaPbPON systems. Unlike lead in oxynitride glasses, tin affects the nitridation mechanism by limiting the nitrogen/oxygen substitution in the anionic network, so that the substitution model is assumed to be closer to the one taking place in alkali phosphate glasses LiNaPON.     

Electrical and optical properties of binary glasses from the arsenictelluriumselenium system

An investigation of binary glasses derived from the arsenicseleniumtellurium system is described in which measurements were made of d.c. conductivity over a range of temperatures, space charge limited current, density and absorption in the near infrared region. For the higher temperature region the electrical results were consistent with conduction being due to carriers excited into extended states. While conduction at lower temperatures may in some cases be due to carriers hopping in localized states at the band edges, an alternative approach in which the localized states were considered to act as donors and acceptors gave satisfactory agreement with the experimentally determined conductivity versus temperature and activation energy versus temperature relationships and with the value of the pre-exponental constant in the conductivity expression. An anomalous field dependence of conductivity was found for annealed specimens of two glasses and it is tentatively suggested that this is associated with the creation of an impurity band. Measurements of space charge limited current showed that gold gave ohmic contacts to the glass, whereas silver and copper did not. The measurements also provided evidence for the localized states having an exponential distribution. Changes of electrical properties and density as a function of glass composition are discussed in the light of possible structural changes taking place in the glasses. The absorption edges of the glasses in the infrared region were found to be exponential in form and had slopes that did not very greatly for the range of compositions studied.     

The mixed alkali effect in sodium and potassium galliosilicate glasses II. DC electrical conductivity

The DC electrical conductivities of several series of mixed alkali galliosilicate glasses have been measured. The appearance of a minimum in the electrical conductivity of these glasses, independent of the gallium content, suggests that the mixed alkali effect is independent of the non-bridging oxygen content. These results are discussed in terms of current theories proposed to explain this anomalous behaviour.     

Rheological properties of potassium barium borate glasses

Several series of potassium barium borate glasses have been investigated as to their rheological properties.It has been found, that all these glasses show deviations from ‘Newtonian’ behaviour below temperatures corresponding to viscosities of 10¹⁰ poises. The activation energies of viscous flow are linear in both the potassium and barium mole percentages.For the ternary systems the pre-exponential factors of the viscosities do not decrease considerably with increasing metal ion content, contratry to what has been found in binary systems.     

Defect model for the mixed mobile ion effect

This paper presents a new defect model for the mixed mobile ion effect. The essential physical concept involved is that simultaneous migration of two unlike mobile ions in mixed ionic glass is accompanied by expansion or contraction of the guest-occupied sites with distortion of surrounding glass matrix; in many cases, an intensity of the local stresses in glass matrix surrounding ionic sites occupied by foreign ions is much greater than, or at least comparable to the glass network binding energy. Hence, when the stress exceeds the breaking threshold, relaxation occurs almost immediately via the rupture of the bonds in the nearest glass matrix with generation of pairs of intrinsic structural defects. The specificity of the mechanism of defect generation leads to the clustering of negatively charged defects, so that rearranged sites act as high energy anion traps in glass matrix. This results in the immobilization of almost all minority mobile species and part of majority mobile species, so mixed mobile ion glass behaves as single mobile ion glass of much lower concentration of charge carriers. Generation of defects leads also to the depolymerization of glass network, which in turn results in the reduction of the glass viscosity and T_g as well as in the compaction of glass structure (thermometer effect). In the spectra of mechanical losses of mixed alkali glasses it reflects as a shift of the maximum in mechanical losses corresponding to the glass transition to lower temperatures, and the dramatic increase of the maximum corresponding to the movement of non-bridging oxygens (so-called mixed alkali peak). The magnitude of the mixed mobile ion effect is defined by the size mismatch of unlike mobile ions, their total and relative concentrations, the binding energy of the glass-forming network, and temperature. Although the proposed model is based upon the exploration of alkali silicate glass-forming system, the approach developed here can be easily adopted to other mixed ionic systems such as crystalline and even liquid ionic conductors.     

Electrical properties of copper phosphate glasses II. Dielectric properties

The ac and dc electrical properties of the P₂O₅BaOCuO glass system have been measured.TSPC and TSDC experiments and dc conductivity as a function of time indicate the predominantly electronic character of these glasses. The conduction process can be basically explained by a polaron hopping model in an adiabatic regime. Conductivity values which depend on the glass microstructure and switching phenomena are observed. The filamentary-feature of this process suggests a Poole-Frenkel mechanism.A Debye dielectric relaxation non-simple process is deduced from the frequency and temperature dependence of loss tangent and dielectric constant. The activation energies agree with those determinated from dc measurements, suggesting a unique electronic hopping conduction mechanism in both regimes.The ac and dc electrical properties are strongly affected by the glass composition and essentially by the redox Cu⁺/Cu_t ratio.A conduction model accounting for ac and dc behaviour is finally proposed.     

Correlation effects on alkali ion diffusion in binary alkali oxide glasses

The correlation factor in the Nernst-Einstei equation for low sodium Na₂OGeO₂ glass determined from dc conductivity and ²²Na diffusion coefficient measurements was found to be near unity. Values of the correlation factor were also compiled from the literature for higher alkali content germanate glasses as well as for sodium borate and alkali silicate glasses. In all three systems the correlation factor was found to depend primarily on the alkali content in the glass. Specifically, uncorrelated ionic diffusion ($\text{? ? 1}$) occurs in low alkali glasses while correlated motion ($\text{? < 1}$) takes place at higher alkali concentrations. This observation is consistent with the theory that many “holes” exist in low alkali glasses through which the diffusing cation can randomly jump.     

Heat capacities and thermal behavior of alkali borate glasses

The heat capacities of selected glasses in the five alkali borate systems have been measured over a range of high temperatures which includes the respective glass transition regions. The heat capacities per gram atom at 350°K show little variation with composition while those at the low temperature ends of the glass transition, T_g-, show some systematic variations. When compared with the respective 3R values, the heat capacities at T_g- range from about 0.75 for B₂O₃ to values in excess of unity for various alkali borate compositions. The present data on heat capacity have been combined with previous data on the elastic moduli, densities and thermal expansion coefficients to evaluate the Grüneisen constant, γ, for each composition for temperatures around ambient. For B₂O₃, γ has a low value of about 0.25. It decreases with additions of Li₂O and increases with additions of the other alkali oxides.     

Thermal conductivity and specific heat of tellerium-based chalcogenide glasses

The specific heat and thermal conductivity of tellerium-based chalcogenide glasses are reported, together with their glass transition and synthesizing temperatures. The thermal conductivity has been measured in the temperature range between 100 and 500 K while the specific heat was determined at temperatures between 373 and 600 K. Below the glass transition temperature, both physical parameters were observed to be temperature independent.