On the electrochemical behaviour of undercooled melts and glasses

The electrochemical behaviour of undercooled melts and glasses is considered in detail. First the thermodynamic properties of the corresponding phases are calculated and then the temperature course of the emf and of other thermodynamic functions of a galvanic cell in which the net reaction is: undercooled melt (glass)→crystal, are determined. Some additional problems concerning the electrochemistry of amorphous electrodes are analyzed, e.g. hydrogen overvoltage upon hydrogen evolution on crystalline or amorphous electrodes of a given metal. Several variants are discussed for the possible experimental realization of a galvanic cell in which the emf is determined by the difference in the chemical potentials of the undercooled melt (or the glass) and the crystal, i.e. of a galvanic cell with a vitreous and a crystalline electrode made of one and the same electronic conductor or of a bipolar cell with an amorphous and a crystalline electrolyte, etc. An attempt is made to estimate the interal electric (Galvani) potential at the melt/crystal interface by using data for the difference of the Peltier coefficient between the respective phases.The analysis of the electrochemical behaviour of vitreous, liquid and crystalline electrodes is performed on the basis of formal thermodynamics and in terms of classical model approaches. It is shown how to determine by electrochemical measurements the main thermodynamic parameters of glasses which are considered as frozen-in non-equilibrium systems.     

Effect of strontium substitution on the structure,ionic diffusion and dynamic properties of 45S5 Bioactive glasses

Strontium ions can promote bone growth and enhance bioactivity in bioactive glasses that find critical biomedical applications. In this paper, the effect of SrO/CaO substitution on the structure, ionic diffusion, and dynamic properties of 45S5 bioactive glasses has been studied using constant pressure molecular dynamics simulations with a set of effective partial charge potentials. The simulated structure models were validated by comparing with experimental neutron diffraction results. It was found that the SrO/CaO substitution leads to an increase of glass density and decrease of oxygen density, a measure of compactness of the glass, in excellent agreement with available experimental data. On the other hand, the substitution does not significantly change of the medium range glass structures as characterized by silicon and phosphorous Q_n distributions, network connectivity, and ring size distributions. The diffusion and dynamic behavior of these glasses and their melts were also determined by calculating the mean square displacements and velocity autocorrelation functions. It was found that the diffusion energy barriers of sodium, calcium and strontium ions remain nearly constant with respect to the level of substitution. However, strontium ions do influence the diffusion behaviors of calcium and sodium ions at high temperature, as evidenced from their velocity autocorrelation functions. Like calcium and sodium, strontium ions only contribute to the lower frequency (around 100 cm^? 1) of the vibrational spectra the substitution has little effect on high frequency features and the general shape of the vibrational density of states. These results suggest that the increase of the dissolution rate in strontium containing glasses are mainly due to the increase of free volume and the non-local effect that weakens the silicon-oxygen network due to strontium ions.     

Formation and structure of ionic (Na, Zn) sulfophosphate glasses

Supercooled ortho- and pyrophosphate melts of the type P₂O₅-EO-A₂O (E = {Zn²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Mg²⁺, Mn²⁺}; A = {Li⁺, Na⁺, K⁺}) exhibit unusually high sulfate solubility. This enables facile fabrication of low-melting sulfophosphate glasses with SO₃ content of up to 25 mol.%. Sulfur is incorporated into those glasses practically exclusively in the form of isolated SO₄^2- groups. The Q-group distribution of phosphate species is dominated by Q¹ and Q⁰ groups, whereby replacing P₂O₅ with SO₃ results in increasing depolymerization. In this way, the glass forming region can readily be extended to compounds with an average number of bridging oxygen per phosphate anion of less than 0.5. In ionic (Na, Zn) sulfophosphate glasses, cations Zn²⁺ and Na²⁺ appear to cluster distinctively around PO₄^3- and SO₄^2- groups, respectively.     

The review of possible interrelations between ionic conductivity, internal friction and the viscosity of glasses and glass forming melts within the framework of Maxwell equations

The review contains the results of application of Maxwell equations for mechanical relaxation and electrical conductivity, to the systematization of large amount of experimental data related to mechanical, viscous, and electrical properties of inorganic glasses and glass forming melts. The generalization of internal friction results shows the existence of characteristic values for the ratios of temperatures, responsible for α-, β- and ionic relaxations; they are independent on the frequency and chemical composition. This is the evidence for the main role of elastic deformations at various corpuscular processes and the existence of characteristic scale of activation barriers predetermined by local volumes of deformation. It is shown the possibility of very precise calculation of the temperature of “ionic” internal friction maximum for one-alkali oxide glasses directly from Maxwell equation and d.c. conductivity experimental data. The volumes of particles overcoming the potential barrier at viscous flow practically coincide with the results of direct structural determinations. The existence of universal relation between d.c. conductivity and viscosity for the extremely wide temperature intervals (Littleton relation) is proved for silicate and phosphate melts. The theory of this dependence is proposed. The results show the effectiveness of the attempts to unite the continual and discrete approaches within the framework of Maxwell equations to obtain the simplest understanding the mechanisms of different types of relaxation. The review comprises many Russian papers unknown in English scientific literature.     

Molar volume,glass-transition temperature,and ionic conductivity of Na- and Rb-borate glasses in comparison with mixed Na–Rb borate glasses

Mass densities, molar volumes, glass-transition temperatures, and ionic conductivities are measured in series of YNa₂O · (1 − Y)B₂O₃ glasses, with Y = 0.00, 0.04, 0.08, 0.12, 0.16, 0.20, 0.25, 0.30 and YRb₂O · (1 − Y)B₂O₃ glasses, with Y = 0.00, 0.12, 0.16, 0.20, 0.25, 0.30. Measurements of the molar volumes indicate that the incorporation of rubidium ions leads to a considerable expansion of the network, which is not observed for sodium ions. The glass-transition temperature increases with increasing alkali content and reaches a maximum near Y = 0.25 for both glass systems. These trends are attributed to changes in the glass network. For each glass composition an Arrhenius-activated increase of the product of dc conductivity and temperature is observed. The activation enthalpy decreases with increasing number density of ions. A comparison between the binary sodium- and rubidium-borate glasses from this work, with the ternary sodium–rubidium borate glasses studied earlier in our laboratory, provides interesting insights in the influence of the glass structure on ionic transport processes and the mixed-alkali effect.     

Structural changes of Ag+–Na+ ion exchanged soda-lime glasses investigated by scanning electron microscopy and infrared reflectivity

The combination of infrared spectroscopy and scanning electron microscopy allowed the monitoring of the structural changes of a soda-lime glass submitted to increasing durations of Ag⁺–Na⁺ ion exchange in a molten salt bath at 350 °C. Both techniques show an insertion of silver ions in the glass structure that is about 10% higher than the departure of sodium ions. The electro neutrality of the compounds is preserved with local alterations which lead to a higher degree of depolymerization of the silicate network. During the exchange process only sodium leaves the matrix and its content does not go beyond a threshold of about 50% of the initial content.     

Thermal analysis, fragility and viscosity of Au-based metallic glasses

Metallic glasses based on Au of composition Au₄₉Cu_26.9Ag_5.5Pd_2.3Si_16.3 and (Au₄₉Cu_26.9Ag_5.5Pd_2.3Si_16.3)₉₉X₁ where X = Ti and In, have been produced and characterized in ribbon form. They show a glass transition and a rather wide undercooled liquid region before crystallisation.The fragility index (m) of the alloys was investigated with two methods involving differential scanning calorimetry (DSC) measurements. In one method the glass transition temperature was determined at different scanning rates in the range 0.3-100 °C/min and its trend fitted to give m. In the other m was obtained from the temperature span of the glass transition range at the scanning rate of 20 °C/min. Implications for viscosity in the undercooled liquid are derived and thoroughly discussed ending with a VFT (Vogel-Fulcher-Tammann) expression for it.     

Characterization of the diffusion process in oxide glasses based on the correlation between electric conduction and dielectric relaxation

Electric conduction was correlated with dielectric relaxation for many ionically and electronically conducting oxide glasses. On the basis of this correlation, the carrier-diffusion process occurring in the glasses was identified. Of the three types of diffusion processes (localized diffusion process, non-localized diffusion process I and non-localized diffusion process II) one or more were found in each glass. The diffusion process shifted from one type to another with varying glass composition in certain series of glasses. The conditions of preparation of the glasses were found to influence the diffusion processes in these glasses. These facts are discussed in terms of the ‘microstructure’ of glass.     

Effect of Al2O3 on the viscosity and structure of calcium silicate-based melts containing Na2O and CaF2

The effect of Al₂O₃ on viscosity in the calcium silicate melt-based system containing Na₂O and CaF₂ was investigated and correlated with the melt structure using FTIR (Fourier transform infrared) spectroscopy, XPS (X-ray photoelectron spectroscopy), and Raman spectroscopy. Substituting SiO₂ with Al₂O₃ modified the dominant silicate network into a highly structured alumino-silicate structure with the aluminate structure being particularly prevalent at 20 mass% of Al₂O₃ and higher. As the melts become increasingly polymerized with higher Al₂O₃ content, the fraction of symmetric Al–O⁰ stretching vibrations significantly increased and the viscosity increased. XPS showed a decrease in the amount of non-bridged oxygen (O^?) but an increase in bridged oxygen (O⁰) and free oxygen (O^2?) with higher Al₂O₃. Although changes in the structure and viscosity with higher CaO/(SiO₂ + Al₂O₃) were not significant, the symmetric Al–O⁰ stretching in the [AlO₄]^5?-tetrahedral units decreased. The apparent activation energy for viscous flow varied from 118 to 190 kJ/mol.     

Density, viscosity and surface tension of 50RO-50P2O5 (R: Mg, Ca, Sr, Ba, and Zn) glass melts

The density, surface tension and viscosity of the 50RO-50P₂O₅ (R: Mg, Ca, Sr, Ba and Zn) glass melts have been measured over the range, 1073-1623 K. The effects of R cations on these properties have been investigated. The density of the melt was found to increase in the order, R: Mg<Ca<Zn<Sr<Ba, with increasing molar weight of cation. The surface tension in the temperature range of 1373-1473 K increased approximately with cation in the order, R: Zn<Ba<Mg<Ca<Sr. The viscosity and the negative, temperature coefficient of surface tension increased in the order, R: Ba<Sr<Ca<Zn<Mg. All melts exhibited negative temperature coefficients of surface tension. The effect of Mg and Zn cations on the properties were different to that for Ba, Sr, and Ca cations and this is discussed using bulk glass data published in a previous report. The features of Mg and Zn metaphosphate glass melts, that is high values of viscosity, and temperature coefficient of surface tension, are related to the small Oxygen Coordination Number of the cations (=4) when compared with those of Ca, Sr, Ba metaphosphate glass melts.     

Incorporation of water into glasses and its influence on the diffusion of cations,including the creation of diffusion barriers

When heated to elevated temperatures, many glasses take up water from moisture-containing environments. This leads not only to changes in local water concentrations, but also to non-uniform structural changes within the glass. These structural changes impact many structure-sensitive properties, including the diffusivity of ions. Experimental data for the uptake of water by a Type I silica glass, Infrasil 302, and by an alkaline-earth boroaluminosilicate glass, Corning Code 1737, are discussed as well as the influence of the incorporation of water into these glasses on the diffusion of sodium. Furthermore, the modification of glass near the surface by the uptake of water, leading in the case of the alkaline-earth boroaluminosilicate glass to the creation of a very effective barrier layer against the diffusion of sodium, is addressed.     

Relationship between density,viscosity and structure of GeO2 melts at low and high pressures

A correlative study of the viscosity, density and structure of GeO₂ melts has been carried out at low and high pressures. It is observed that under isothermal (1425°C) conditions the viscosity decreases from 6.0 × 10³ poise at 1 bar to 1.2 × 10³ poise at 9.5 kbar. The maximum variation in the density of quenched GeO₂ glasses is from 3.62 ± 0.02 g cm^?3 for glass formed from a liquid quenched at 1 atm and 1425°C to 3.95 ± 0.04 g cm^?3 for glass formed from a liquid quenched at 18 kbar and 1700°C.The similarity of the Raman spectra of GeO₂ melt quenched at 1 atm (1425°C) and at 18 kbar (1700°C) implies that the scattering units in GeO₂ glasses quenched at low and high pressures are the same. The intensity of the Rayleigh tail, however, decreases in glasses quenched at successively higher pressures, the structure apparently becoming more ordered with increasing pressure. The Raman spectra of the GeO₂ polymorphs with quartz and rutile structures, crystallized at 1150°C and at 4 and 6 kbar, respectively, are distinct because of the difference in Ge coordination, resulting in a large difference in the frequency and intensity of the GeO symmetric stretching mode in the two polymorphs. A comparison of the Raman spectra of GeO₂ glasses with those of crystalline GeO₂ polymorphs shows that the local ordering in GeO₂ glass is similar to that of hexagonal GeO₂ in which Ge is tetrahedrally coordinated.The decrease in the viscosity of GeO₂ melt with increasing pressure cannot be attributed to a pressure-induced coordination change [1]. More likely, there is a systematic change in the nature of the GeO bond with increasing pressure. The increase in the degree of local ordering in GeO₂ melts quenched at high pressures does explain the progressive increase in melt density.     

Elastic constants,hardness and their implications to flow properties of metallic glasses

The longitudinal and transverse sound velocities and Vickers hardness of metallic glasses (Pd_{1 ? x}Ni_x)_0.80P_0.20, (Pd_{1 ? x}Fe_x)_0.80P_0.20 and (Pt_{1 ? x}Ni_x)_0.75P_0.25 have been measured. The elastic constants at room temperature exhibit a positive deviation with composition χ from linearity whereas the hardness shows a negative deviation. The increase in elastic constants has been attributed to a denser packing of the alloys on mixing. The reduced hardness H_rH/μ versus χ exhibits a remarkable similarity to a T_g versus χ relationship. This seems to indicate that flow mechanisms involved in metallic glasses above and below the glass-transition temperature are of similar origins. It is the excess entropy of disorder associated with alloying which lowers the hardness as well as the viscosity of metallic glasses. The metallic glasses possess in general a relatively high Poisson's ratio ν ≈ 0.40 and a shear modulus approaching that of the noble metals Cu, Ag and Au. Among the metallic glasses observed, the PtP glasses exhibit the highest ν = 0.42, whereas the glasses containing Fe tend to have lower values. The phenomenon that the conduction electrons in the glassy alloys behave as in the noble metals may be partly attributed to the filling of d shell orbitals of the transition metals in the PtP, PdP and NiP alloys. The high ν of metallic glasses is believed to be responsible for the ductile behavior of these glasses. Poisson's ratio ν of metallic glasses was observed to decrease with decreasing temperature. It is suggested that the decreasing ν with falling temperature causes the rapid increase in the fracture strength of Fe-based glasses.     

High pressure effects on liquid viscosity and glass transition behaviour,polyamorphic phase transitions and structural properties of glasses and liquids

Since the pioneering work of Bridgman it has been known that pressure affects the glass transition of polymers and liquid state viscosities. Usually the T_g and viscosity both increase as a function of pressure as expected from ‘free volume’ theories. However, H₂O provided a notable exception in that the viscosity passes through a minimum at low temperature. It was thought that this might be linked to the anomalous thermal expansion behavior. However further research on geologically important aluminosilicate liquids revealed that they could show anomalous viscosity decreases with increasing pressure and this behavior is given a structural interpretation as five-fold coordinated Si⁴⁺ and Al³⁺ species are formed. Also the existence of polyamorphism or density-driven liquid–liquid phase transitions in certain systems can lead to anomalies in the T_g or η vs. P relations. This may be the case for H₂O, for example. Current research is focusing on investigating structural changes in liquids and glasses at high pressure as the rich variety of behavior is becoming recognized. Both experimental studies and computer simulations are important as the underlying phenomonology is linked to changes in the glass or liquid structure as a function of densification.     

Silver sulfide based glasses (I). Glass forming regions,structure and ionic conduction of glasses in GeS2Ag2S and GeS2Ag2SAgI systems

Ag₂S forms with GeS₂ stable glasses over a wide range of compositions (0–55% Ag₂S mol%). In the same system, more complex glasses obtained by dissolving silver iodide have been synthesized with up to 50 mol% AgI.Raman spectra are presented and a vibrational assignment in terms of bridging and non-bridging sulfur has been made. The electrical conductivity of these glasses has been measured over a temperature range (?50°C? + 50°C) and for various compositions by the complex impedance diagram method. At 25°C, the conductivity reached a maximum value of 6 × 10^?3 Ω^?1 cm^?1. Whatever the glass used, the same limit value of conductivity $\text{(σ ? 10 su?2 Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$) and activation energy ($\text{E}{}_{\mathrm{\sigma }}\text{? 0.25}\text{eV}$) are obtained for the highest content of silver iodide. A conduction mechanism is proposed.     

Effects of cation field strength on the structure of aluminoborosilicate glasses: High-resolution B, Al and Na MAS NMR

Among the most important adjustable compositional variables in controlling glass and glass-melt properties are the relative proportions of network modifiers with varying cation field strength (ratio of charge to radius). Here we determine the details of structural changes caused by variations in the ratio CaO/Na₂O in two series of aluminoborosilicate glasses with different contents of boron oxide. Using high-resolution, high field ¹¹B and ²⁷Al MAS NMR, we report precise values of contents of three- and four-coordinated boron (N₄) and of four- and five-coordinated aluminum (^[5]Al), and calculate fractions of non-bridging oxygens (NBOs). Increasing CaO/Na₂O dramatically lowers N₄ and increases NBO and ^[5]Al, but effects are non-linear with composition. Boron content affects these trends because of energetic constraints of mixing of various network cations. ²³Na spectra reveal slight but systematic increases in the mean Na-O distance with increasing CaO/Na₂O, suggesting that in Ca-rich glasses, Na⁺ has a higher ratio of bridging to non-bridging oxygens in its coordination shell. All of these changes can be understood by the tendency of higher field strength modifier cations to promote the concentration of negative charges on non-bridging oxygens in their local coordination environment, systematically converting four- to three-coordinated boron.     

The effect of hydrostatic pressure on the dielectric constants, and their temperature dependences, of phosphate and tellurite glasses

Measurements of the pressure dependence of the static dielectric constant of tellurite (pure TeO₂ and 67%TeO₂ + 33%WO₃) and samarium phosphate (5%Sm₂O₃ + 95%P₂O₅ and 15%Sm₂O₃ + 85%P₂O₅) glasses at elevated pressures (0–70 kbar) for a range of temperatures (77–380 K) are reported. The electrical properties under pressure have been determined from the low-frequency complex plane analysis of glass discs contained within a Bridgman opposed anvil cell. The most notable observation is that the pressure dependence of the static dielectric constant, of all glasses studied, is positive, for example for vitreous TeO₂ ln ε/P is equal to 4.41 × 10⁻¹¹ (Pa⁻¹) at 293 K. Behaviour of this type is common to a number of materials (plastics and chalcogenide glasses) for which it is not possible to define any long-range order. It is in direct contrast with the behaviour of crystalline insulators, for which ε/P is usually negative. The effect of pressure on the dielectric constant has been analysed using two different approaches based on the macroscopic Clausius-Mossotti equation. The effects of high pressure on the dielectric constant have been correlated with the temperature dependence of the dielectric constant at atmospheric pressure.     

Synthesis, characterization, and crystal structures of two strained cyclic diacetylenes and their precursors

The synthesis, characterization, and crystal structures of two novel strained cyclic diacetylenes are reported. A discussion is presented about the relative bond distances of the diacetylenes compared to a previously reported strained cyclic diacetylene to further determine the degree of aromaticity of that compound. 1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15,17-pentadehydro[18] annulene (5) is triclinic, P ^–1, with = 9.489(5), b = 10.550(5), c = 12.155(6) Å, = 100.50(4), = 106.50(4), = 100.85(4)°. 1,2:5,6:9,10:13,14:17,18-Pentabenzo-3,7,11,15,19,23,25-heptadehydro[26]annulene (7) is triclinic, P ^–1, with a = 9.611(2), b = 10.388(3), c = 15.963(3) Å, = 88.67(2), = 76.25(1), = 68.69(2). In addition, two precursors of 5, 3 and 4 which have a helical twist, are reported. [1,2-ethynediyl-bis(2,1-phenylene-2,1-ethynediyl-2,1-phenylene-2,1-ethynediyl]bis[trimethyl-silane] (3) is monoclinic, P2₁/c, with a = 13.682(4), b = 9.787(2), c = 13.448(4) Å, = 112.37(2)°. 1,1-(1,2-ethynyldiyl)bis[2-[(2-ethynylphenyl)ethynyl]-benzene (4) is monoclinic, P2₁/n, with a = 15.951(3), b = 3.999(1), c = 18.168(4) Å, = 99.05(3)°.