Ionic conductivity of Li2O-BaO-Bi2O3 glasses

Dc and ac conductivities of Li₂O-BaO-Bi₂O₃ glasses have been studied in a temperature range of 263-523 K and a frequency range of 10 Hz-2 MHz and have been compared with those of binary Li₂O-Bi₂O₃ glasses. The frequency dependent conductivity has been studied employing both the modulus and conductivity formalisms. We have observed small changes in the dc conductivity and its activation energy from those of the binary glass when content of BaO is small. However we have observed noticeable changes in the conductivity and the activation energy when BaO content is large. The significant changes in the values of the non-exponential parameter and the power-law exponent of the ac electrical properties have been observed due to introduction of BaO in the lithium bismuthate glasses. The existing relation between the power-law exponent and the non-exponential parameter was also violated in the present glass compositions.     

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.     

Spectroscopic and dielectric properties of a lithia-containing glass

Glass of the composition 65SiO₂-20CaO-15Li₂O (mol %) was prepared and subjected to heat treatment. The obtained samples were characterized before and after heat treatment by DTA, TG, XRD, SEM, IR and dielectric spectroscopy. DTA showed an endothermic peak at 954 °C, accompanied by a pronounced change in the microstructure, as revealed by SEM. XRD showed that metasilicate predominates on heat treatment at 726 °C, while on heat treatment at 726 °C, then at 954 °C, disilicate crystallizes as the main phase. The IR spectra of the heat-treated glasses revealed that the vibrations of O-H groups are drastically decreased, while those due to non-bridging oxygens Si-O⁻ are increased. The dielectric constant (ε′), the loss tangent (tan δ) and the ac conductivity (σ_ac) for the prepared glasses were investigated before and after heat treatment over a moderately wide range of frequency and temperature. The activation energy of the dielectric relaxation process was found to depend on the techniques of sample preparation. A drop of dielectric constant values was observed for the heat-treated sample, which can be attributed to the ordering of the induced crystalline phases. The conductivity behavior suggests a hopping mechanism responsible for conduction.     

Electrical and dielectric properties of Sb2O3–V2O5–K2O glasses

Electric measurements, including temperature dependencies of direct electrical conductivity and temperature dependencies of complex electrical modulus, have been implemented using Sb₂O₃–V₂O₅–K₂O glass samples. These glasses absorb ambient humidity but their resistance to water attack depends on composition. The significant decrease of conductivity up to 100 °C can arise from water desorption. Cycling measurements of direct electrical conductivity versus temperature were also implemented. They show that the 30Sb₂O₃–30V₂O₅–40K₂O and 70Sb₂O₃–30K₂O glasses are irreversibly damaged with the formation of the hydrated layer. In addition, it was observed that the evolution of DC conductivity is ruled by Arrhenius relation, while activation energy decreases as Sb₂O₃ concentration increases.     

DC conduvtivity of V2O5TeO2 glasses

The dc conductivity of semiconducting vanadium tellurite glasses of compositions in the range 50 to 80 mol% V₂O₅ has been measured in the temperature region 77 to 400 K. Measurements have been made on annealed samples at different annealing temperatures. Annealing the samples at temperature of about 250°C causes the appearance of a complex crystalline phase resulting in an increase of conductivity. Results are reported for amorphous samples of different compositions. The conductivity of tellurite glasses is slightly higher than the corresponding composition of phosphate glasses, but the general trend of the increase of conductivity and decrease of high temperature activation energy with increasing V₂O₅ content is similar in the two systems. The data have been analysed in the light of existing models of polaronic hopping conduction. A definite conclusion about the mechanics of conduction (adiabatic or nonadiabatic) is difficult in the absence of a precise knowledge of the characteristic phonon frequency v₀. Adiabatic hopping is indicated for v₀～10¹¹ Hz, however this value leads to unreasonably low value for the Debye temperature θ_D, and higher values for v₀～10¹³ hz satifiies the conditions for nonadiabatic hopping which appears to be the likely mechanism of conduction in V₂O₅TeO₂ glasses. The low temperature data (< 100 K) can be fitted to Mott's variable range hopping, which when combined with ac conductivity data gives reasonable values of α, but a high value for the disorder energy.     

Structural implications of water and boron dissolution in albite glass

A combined nuclear magnetic resonance, infrared and Raman spectroscopic study on the effect of water dissolution on the structure of B-bearing aluminosilicate glasses is presented. The base composition was albite (NaAlSi₃O₈) to which different amounts of B₂O₃ (4.8, 9.1, 16.7 wt%) were added. Hydrous glasses containing 4.4 ± 0.1 wt% water were synthesized at pressures of 2000 bar. The results show that B dissolves in both dry and hydrous glasses by forming predominantly trigonal BO₃ groups although some tetrahedral BO₄ is also present. In anhydrous glasses prepared at high pressures (above 10 kbar) the fraction of BO₄ increased. The hydrous glasses contain more BO₄ groups compared to the dry counterparts, suggesting that this species is stabilized by water. The Raman and NMR (¹⁷O, ²⁷Al, ²⁹Si) spectra show that B interacts with the aluminosilicate network by formation of Si-O-B and probably Al-O-B units. In the hydrous glasses the water speciation changes significantly towards higher hydroxyl concentrations with increasing B-content. The NIR peaks, which are related to OH groups and molecular H₂O, develop additional shoulders, suggesting that possibly B-OH complexes are formed.     

The role of water vapour on the oxidation of two Ln-Si-Al-O-N glasses (Ln=Y, La)

The oxidation behaviour of LnSiAlON (Ln=Y, La) glasses was studied at different temperatures (990-1150 °C) and under different water vapour pressures (360-2690 Pa). These results were also compared with those obtained under O₂, N₂/H₂O or O₂/H₂O mixtures. When glasses are treated under a N₂/H₂O mixture, optical and SEM observations show porous scales. Transformations of the reaction rate data and a kinetic model show that there is only one limiting process occurring during oxidation. This rate limiting step is the progress of the chemical reaction at the internal interface. Determination of the pressure law dependence and thermodynamics calculations of water vapour molecules dissociation at the investigated temperatures allow us to suggest that the mechanism of oxidation corresponds to decomposition of water molecules on the oxynitride glass surface.     

Influence of disorder on the diffusion of alkali ions in SiO2- and GeO2-glasses

The frequency factor and activation energy for the diffusion of Na and K in SiO₂-glasses are strongly dependent on the concentration of Na₂O or K₂O respectively. A similar behavior was found for hydrogen diffusion in amorphous metals. In the last case the results are in agreement with theoretical calculations, if a Gaussian distribution of activation energies is assumed which arises from a similar distribution of the potential energy of hydrogen being in equilibrium sites. The equations derived were used in this study to describe the concentration dependence of Na and K diffusion in SiO₂ glasses, because these impurities are dissolved in randomly distributed interstices of different volume as well. The theory yields the two experimental facts that diffusion below the glass transformation temperature is governed by a single activation energy and that concentration profiles of the tracer atoms can be described by a constant diffusion coefficient. A comparison with low temperature results for Na diffusion shows they agree with theoretical predictions and yield the following parameters: most probable value of the activation energy = 59.4 kJ/mol, corresponding frequency factor = 2 × 10^?3 cm²/s and half width of the Gaussian distribution = 25 kJ/mol. The model also predicts a minimum in plots of the chemical diffusivity versus concentration which is in agreement with experimental findings for sodium diffusion in GeO₂.     

Structural and transport properties of quaternary glass system: LiF-Li2O-SrO-Bi2O3

Bismuth based glasses containing LiF, Li₂O and SrO were investigated by different physical, spectroscopic and transport techniques. The results show that density of the glass system increases whereas glass transition temperature decreases with increase in LiF content. The decrease in glass transition temperature is attributed to the entry of the fluoride ions into the glass network mainly substitutionally in place of oxygen ion. The increase in dc electrical conductivity in the present glasses with increase in the fluorine ions is due to the mixed contribution of the positively charged lithium cations throughout the glass network and the negatively charged fluorine, which may act as impurity and/or as terminal non-bridging halide ion. Infrared and Raman spectroscopic results indicate that the glass network consists of BiO₆ octahedral and BiO₃ pyramidal units.     

Electrical conductivity and dielectric properties of Bi2O3-GeO2-PbO-MoO3 glasses

Glasses having compositions 40Bi₂O₃-20GeO₂-(40−x)PbO-xMoO₃ (where x = 3, 6, 9, 12 and 15 mol%) were prepared by normal melt quenching technique. The density (d) decreases gradually with the increase of the MoO₃ content in such glasses. This may be due to the lower molecular weight MoO₃ is substituted by a higher molecular weight PbO. The dc conductivity decreases while the activation energy increases with the increase of the MoO₃ content. The dc conductivity in the present glasses is electronic depends strongly upon the average distance, R, between the Mo ions. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron. Dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac, over a range of frequency 0.12-100 kHz and temperature 325-650 K and frequency exponent s) of these glasses have been studied.     

Protonic conduction in alkaline earth metaphosphate glasses containing water

D.c. electrical conductivity data were obtained for M O·P₂O₅ glasses (M = Be, Mg, Ca, Sr, Ba) containing small amounts of water. The results suggest that the mobility of protons in the glasses increases with decreasing OH bonding strength. The relation between the proton concentration and the conductivity or the apparent activation energy was studied for calcium metaphosphate glasses containing various amounts of water. The conductivity was found to be proportional to the square of the proton concentration; the apparent activation energy decreased linearly with increasing logarithm of proton concentration.     

Potential energy landscape of Li+ ions in lithium silicate glasses: Implications on ionic transport

The potential energy landscapes of Li⁺ ions in Li₂O–SiO₂ glasses containing 3.3–15 mol% Li₂O have been studied using molecular dynamics simulation. It is shown for the first time that the densities of states for Li⁺ ions follow a nearly universal logarithmic distribution irrespective of the Li concentration. Such a functional form of the ionic density of states is shown to provide an explanation for the experimentally observed logarithmic dependence of the activation energy of dc conductivity on the modifier ion concentration in a wide variety of glasses.     

DC electrical conductivity of semiconducting cobalt-phosphate glasses

The dc conductivity of semiconducting cobalt-phosphate glasses has been measured at temperatures ranging from 213 to 530 K. Four bulk samples of CoO-P₂O₅ glasses of different compositions were produced by melting dry mixtures of analytical reagent grades of CoO and P₂O₅ at temperatures between 1200-1250 °C for 2 h using a press-quenching method from glass melt. Samples were annealed at 400 °C for 1 h. The dc conductivity was found to be dependent on the CoO content in the glass. At temperatures from 213 to 444 K, however, both Mott's variable-range hopping (VRH) and the Greaves' intermediate range hopping models are found to be applicable. VRH at this range of temperatures is attributed to large values of the disorder energy of these glasses.     

Viscosity and glass transition temperature of hydrous float glass

Viscosity of water-bearing float glass (0.03-4.87 wt% H₂O) was measured in the temperature range of 573-1523 K and pressure range of 50-500 MPa using a parallel plate viscometer in the high viscosity range and the falling sphere method in the low viscosity range. Melt viscosity depends strongly on temperature and water content, but pressure up to 500 MPa has only minor influence. Consistent with previous studies on aluminosilicate compositions we found that the effect of dissolved water is most pronounced at low water content, but it is still noticeable at high water content. A new model for the calculation of the viscosities as a function of temperature and water content is proposed which describes the experimental data with a standard deviation of 0.22 log units. The depression of the glass transition temperature T_g by dissolved water agrees reasonably well with the prediction by the model of Deubener [J. Deubener, R. Müller, H. Behrens, G. Heide, J. Non-Cryst. Solids 330 (2003) 268]. Using water speciation measured by near-infrared spectroscopy we infer that although the effect of OH groups in reducing T_g is larger than that of H₂O molecules, the difference in the contribution of both species is smaller than predicted by Deubener et al. (2003). Compared to alkalis and alkaline earth elements the effect of protons on glass fragility is small, mainly because of the relatively low concentration of OH groups (max. 1.5 wt% water dissolved as OH) in the glasses.     

Sodium tracer diffusion in glasses of the type (Na2O)0.2[(BO1.5)x(SiO2)1 − x]0.8

Sodium tracer diffusion coefficients, D_Na*, have been measured in sodium borosilicate glasses of the type (Na₂O)_0.2[(BO_1.5)_x(SiO₂)_1 − x]_0.8 as a function of temperature and the composition parameter x. In these glasses, which can alternatively also be described by using the formula Na₂O·(2B₂O₃)_x·(4SiO₂)_1 − x, one network former unit, SiO₂, is replaced by another one, BO_1.5, while keeping the sodium concentration constant. At constant temperature, the tracer diffusion coefficient of sodium as a function of x has a shallow minimum at about x = 0.7. At temperatures below about 310 °C the temperature dependences of the measured tracer diffusion coefficients are of Arrhenius-type; at higher temperatures one observes an increase in the temperature dependence with increasing temperature. The activation energy derived from sodium tracer diffusion data for temperatures up to about 310 °C increases about linearly with increasing x from about 70 to 80 kJ/mol. The pre-exponential factor as a function of x varies by about one order of magnitude and has a minimum at about x = 0.4. Values derived for the Haven-ratio are smaller than one and show a shallow minimum as a function of x at around x = 0.75. Furthermore, it was investigated whether there is a significant, directly measurable uptake of water during annealing in moist atmospheres and whether water taken up from moist atmospheres can influence the diffusion of sodium.     

Ac conductivity of Ag-doped bulk,glassy As2S3

Measurements of the electrical conductivity of Ag-doped bulk As₂S₃ glasses have been made as functions of temperature, pressure, frequency and Ag doping level. A Debye-like loss peak was observed near 10⁴ Hz. The frequency of the loss peak is dependent on temperature, pressure and doping level, but these dependences are different from those of the dc conductivity. The ac loss is attributed to the Maxwell-Wagner losses characteristic of inhomogeneous materials. The materials are presumed to be inhomogeneous mixtures of As₂S₃ and Ag₂S. We have also searched unsuccessfully for ac conductance in several bulk chalcogenide glasses.     

Molybdenum doping of semiconducting vanadium phosphate glasses

The DC conductivity and dielectric properties of glasses of composition (70 ? x) V₂O₅ : x MoO₃ : 30 P₂O₅ have been measured as a function of temperature and frequency for O × 5 mol %. An increase in conductivity by two orders of magnitude is observed for 1 mol % MoO₃ and this is correlated with changes in activation energy and dielectric constant. The results can be explained in terms of small polaron theory, with the main interaction being through the local electronic polarizability at any site. The results indicate that percolation considerations have to be taken into account in describing the electrical properties of transition metal glasses.     

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.     

Ionic transports and optical spectra of 50Li2O–50B2O3 glass

The ionic and optical transports of 50Li₂O–50B₂O₃ glass were investigated. Time-resolved current spectra (TRCS) showed repetitions of typical charge and discharge processes. The model circuit and equation for the TRCS and the equation for the relation between the turning times of polarization (TTP) and configuration energy (CE) have also been suggested. Equations were satisfied by the experimental results, and the potential and temperature dependence of the configuration energy (CE) and the dipole length from the TTP were investigated in detail. Kink phenomena showed that three or more types of charges were involved in the polarizations. The bi-exponential conductivity equation was applied to obtain the temperature dependence of the ac conductivity (TDAC). Complex impedance spectra (CIS) consisted of a semi-arc and a spur due to the electrode-specimen polarization. The shift of inflection points and peak frequencies in complex modulus spectra (CMS) showed non-Debye type relaxations, and the activation energy for relaxation was consistent with the relaxation for the temperature dependence of the dc conductivity (TDC). The migration concept (MC) applied to the CMS was satisfied at the dispersion and peak region, but slightly swerved at the tail. The fractal dimensionality displayed a three-dimensional character. The band gap, Urbach energy and optical indexes were obtained from optical spectra using Kramers–Kronig analysis (KKA).     

Crystal growth of boron monophosphide using a B2H6-PH3-H2 system

Boron monosphide (BP) with (100) orientation can be epitaxially grown on Si substrates with (100) orientation by thermal decomposition of B₂H₆ and PH₃ in hydrogen. In a horizontal CVD system, the growth rate was studied as a function of gas phase composition and temperature. The growth rate is independent of the PH₃ partial pressure in the region where the PH₃ is in excess. For low values of the B₂H₆ partial pressure the growth rate is proportional to the B₂H₆ partial pressure (a linear region) with an activation energy of 1.8 eV, and for high values of the B₂H₆ partial pressure the growth rate becomes constant (a saturation region) with an acivation energy of 3.0 eV. A simple adsorption-reaction model can be proposed to explain the experimental growth kinetics. The conductivity of the as-grown layer is determined by the PH₃ partial pressure. n-type BP can be obtained for high values of the PH₃ partial pressure and p-type BP for low values. Si doping during the growth and phosphorus anti-site donors are two possibilities to explain the results.