The Raman coupling function in v-GeO2 and v-SiO2: A new light and neutron scattering study

We report inelastic Raman and neutron scattering spectra for the network glass formers vitreous silica (v-SiO₂) and vitreous germania (v-GeO₂) measured at temperature from 10 to 300 K. The ability to determine the temperature dependence of the luminescence background in Raman scattering has allowed to obtain the Raman coupling function C(ω) and in particular, its low-frequency limit. This study indicates that C(ω) has a linear behavior near the Boson peak maximum and below.     

Raman line shape analysis as a mean characterizing molecular glass-forming liquids

Raman scattering spectra in glass forming toluene were studied in the temperature range 50–323 K with the goal of extracting information about homogeneous, inhomogeneous and orientational broadening. It was found that the temperature dependence of inhomogeneous line width allows one to depict two peculiar temperatures: T_A and T_g, where T_g is the glass transition temperature and T_A is the temperature of transition from an Arrhenius-like to a non-Arrhenius behavior for the α-relaxation time dependence on temperature, τ_α(T). Temperature dependence of the orientational phase loss time τ_OPL was found to correspond well to τ_α at T > T_A and continues approximately Arrhenius behavior for lower temperature in contrast to τ_α(T). Also, a comparative analysis of homogeneous broadening of polarized and depolarized lines was done, which provided an estimation of the orientational broadening γ_NL(T). The found γ_NL(T) decreases linearly as the temperature decreases and goes to zero at T ~ T_c, where T_c is the critical temperature in framework of the mode-coupling theory (note that T_c is close to other peculiar temperatures T_B and T_β, but we did not intent to distinguish among them in the present work). Thus, it was shown that the Raman line shape analysis in molecular glass forming materials allows one to extract peculiar temperatures: T_A, T_g, and, probably, T_c.The test of the possibility to use a probe molecule for the Raman line shape analysis has revealed that the extracted data for probe molecule lines do not characterize the host matrices, at least in the low-viscous state (T > T_A).     

Formation and stability of amorphous molecular systems: As the prototype of functional amorphous organic materials

Structural changes in vapor-deposited amorphous states of simple organic compounds were studied by Raman scattering, X-ray diffraction, and light interference in the sample. Two types of processes, namely direct crystallization and structural relaxation leading to glass transition, were observed depending on the flexibility of the molecule. Gradual relaxations were also found to occur in amorphous states of butyronitrile and 1,2-dichloroethane at temperatures much lower than their T_g or crystallization temperature. The observed structural changes are discussed by referring to the high enthalpy of the vapor-deposited amorphous systems.     

Characteristic temperatures of enthalpy relaxation in glass

The glass transition temperature, T_g, directly measured by differential scanning calorimetry at 10 K/min is compared with the T_g indirectly determined by fitting viscosity data to a viscosity model for oxide glasses. The results show good match between the two T_g values. A standard, unified approach for measuring T_g is proposed. Characteristic temperatures of enthalpy relaxation in glass are defined, and the relationships between these temperatures are illustrated by performing aging and calorimetric experiments on hyperquenched glasses. The features of the energy release peak, the endothermic pre-peak, and the real glass transition are discussed with respect to their physical origins.     

Kinetic vs. thermodynamic control of crystal nucleation and growth in molten silicates

A series of calcium aluminosilicate liquids have been experimentally heat-treated at high but variable states of undercooling, from just above the glass transition to the vicinity of the solidus. The mineralogy and chemistry of crystalline phases which appear in these experiments have been quantified using a combination of Transmission Electron Microscopy and Raman spectroscopy. The results show that mineral compositions are highly variable as a function of temperature, but that changes are governed by the contrasting and strongly temperature-dependent mobilities of network-modifying and network-forming cations. Whereas equilibrium crystals form near the liquidus, disordered and non-stoichiometric phases precipitate near the glass transition. Despite this apparently complex situation, the relative importance of thermodynamic and kinetic factors is found to be a single function of T − T_g (where T is temperature and T_g the glass transition temperature), regardless of the silicate composition. The existence of this mastercurve may be used to control the composition of novel composite materials such as glass ceramics.     

On the role of the β process as precursor of the α relaxation in aromatic polyesters

By performing broad band dielectric spectroscopy measurements in a series of amorphous aromatic polyesters we show that different fast modes, contributing to the β relaxation, appear at temperatures below the glass transition temperature, T_g. At high temperatures, (T > T_g) the different β modes tend to merge and the data have to be described by a single β peak. We tentatively assign a molecular origin to each of the different β modes. But also we find a strong connection among the merged β processes and the precursor of the structural α relaxation, implying that this relaxation may posses an important degree of intra-segmental cooperativity.     

Indentation response of glass with temperature

The mechanical response of different glasses to a Vickers indentor has been investigated between room temperature and T_g+50 °C. The permanent deformation, from which hardness is estimated, as well as the brittle fracture characteristics, allowing for an evaluation of the fracture toughness, were measured and analysed. Comparison between a standard float glass and advanced glasses such as chalcogenide (with mainly covalent bonding) and metallic glasses was made to get a more general insight into high temperature indentation behaviour. As temperature increases, the glass response becomes more and more time-dependent, and in the vicinity of T_g the permanent deformation was observed to increase rapidly for all glasses. Further, while the standard float glass showed an enhanced apparent toughness at elevated temperatures due to a brittle to ductile transition, almost no change in apparent toughness was revealed in the GeAsSe glass emphasizing the time-dependent response of glass at elevated temperature.     

Short range order and glass transition in AgIAg2OB2O3 vitreous electrolytes

Several experimental techniques are used to study the short range order, the dynamics and the glass transition in AgIAg₂B₂O₃ compounds. Addition of Ag₂O to B₂O₃, up to [Ag₂O]/[B₂O₃] ?0.5 modifies the borate network by creating a BO₄ unit for each silver added. Addition of AgI decreases the glass transition temperature (T_g) but has only minor effects on the short range structure of the borate network. Silver iodide is partially accomodated in the interstices of the glass network. The relationship among a tentative structural picture, the ion transport phenomena and the low temperature dynamics are discussed.An investigation of the dynamics in the AgI·Ag₂O·2B₂O₃ glass near and above T_g is presented. With NMR techniques, we monitor the onset of tumbling of the borate units and the dynamical effects of crystallization and/or aging of the glass. Hysteresis effects in the ionic conductivity (σ) temperature dependence and the non-Arrhenian behavior of σT near T_g are interpreted in terms of structural modifications occurring at elevated temperatures in the glass.     

Thermal and optical properties of TeO2–ZnO–BaO glasses

We report the results of a systematic study of the thermal and optical properties of a new family of tellurite glasses, TeO₂–ZnO–BaO (TZBa), as a function of the barium oxide mole fraction and compare them with those of TeO₂–ZnO–Na₂O (TZN). The characteristic temperatures of this new glass family (glass transition, T_g, crystallization, T_x, and melting, T_m) increase significantly with BaO content and the glasses are more thermally stable (greater ΔT = T_x ? T_g) than TZN glasses. Relative to these, Raman gain coefficient of the TZBa glasses also increases by approximately 40% as well as the Raman shift from ~ 680 cm^? 1 to ~ 770 cm^? 1. The latter shift is due to the modification of the glass with the creation of non-bridging oxygen ions in the glass network. Raman spectroscopy allows us to monitor the changes in the glass network resulting from the introduction of BaO.     

Controlled crystallization and ionic conductivity of a nanostructured LiAlGePO4 glass–ceramic

A Li_1.5[Al_0.5Ge_1.5(PO₄)₃] glass composition was subjected to several crystallization treatments to obtain glass–ceramics with controlled microstructures. The glass transition (T_g), crystallization onset (T_x) and melting (T_m) temperatures of the parent glass were characterized by differential scanning calorimetry (DSC). The glass has a reduced glass transition temperature T_gr = T_g/T_m = 0.57 indicating the possibility of internal nucleation. This assumption was corroborated by the similar DSC crystallization peaks from monolithic and powder samples. The temperature of the maximum nucleation rate was estimated by DSC. Different microstructures were produced by double heat treatments, in which crystal nucleation was processed at the estimated temperature of maximum nucleation rate for different lengths of time. Crystals were subsequently grown at an intermediate temperature between T_g and T_x. Single phase glass–ceramics with Nasicon structures and grain sizes ranging from 220 nm to 8 μm were then synthesized and the influence of the microstructure on the electrical conductivity was analysed. The results showed that the larger the average grain size, the higher the electrical conductivity. Controlled glass crystallization allowed for the synthesis of glass–ceramics with fine microstructures and higher electrical conductivity than those of ceramics with the same composition obtained by the classical sintering route and reported in literature.     

Characterization of the elasticity and anelasticity of bulk glasses by dynamical subresonant and resonant techniques

The determination of the elastic and anelastic characteristics by means of original non-destructive techniques has been applied to glasses and glass composites in order to link together the macroscopic data with structural aspects. The dynamical Young’s modulus determined by a free resonance technique allows a good accuracy measurement. Some examples concerning oxides, Ge(As)Se or metallic glasses are presented: the abrupt drop of the modulus in the range of the glass-transition temperature T_g is a general observation, which leads us to an attempt at normalization of the curves E versus T on master curves E/E(T_g) versus T/T_g. To study the viscoelastic properties, a low frequency torsional spectrometer is preferentially used to measure the damping due to viscous movements at a microscopic scale. A study of MgSiAlON glasses allows us to show that the intrinsic activation energy is much smaller than the one measured by creep or relaxation tests and that the glassy transition is characterized by a smooth change from vitreous solid (highly correlated) to quasi-liquid behavior; this has been confirmed on a metallic glass.     

A remark on the negative activation volume for defects in solids

The evolution of the aging process of glassy materials quenched from temperatures above their glass transition temperature T_g, when plotting the relaxed enthalpy versus the decrease in volume, leads to a slope comparable to the isothermal compressibility close to T_g. This empirical result was explained in an earlier publication (V. Katsika-Tsigourakou, G. E. Zardas J. Non-Cryst. Solids 356 (2010) 179–180) by means of a thermodynamical model. Here, we show that the same model enables the explanation of the rare cases of negative defect activation in solids.     

A study of the crystallization of two non-crystalline CuZr alloys

Two CuZr alloys, Cu-50 at% Zr and Cu-54 at% Zr, were splat quenched to the non-crystalline state using a piston and anvil device. The glass transition and crystallization temperatures, as well as the enthalpy releases observed during crystallization were measured using differential scanning calorimetry of as-splat specimens and specimens aged below T_g. Transmission electron microscopy and X-ray diffraction experiments were utilized to monitor phase and structural changes in the alloys as they were transformed to the crystalline state.The results of the investigation indicated that the non-crystalline to crystalline transformation of these two alloys in constant heating rate experiments above T_g was a two-step process. The initial step, which is associated with a large exothermic reaction, results in the appearance of crystallites in a matrix of non-crystalline material. The final step, associated with a smaller exothermic reaction, results in the total transformation of glass to the crystalline state and the formation of the equilibium crystalline phases.The effect of aging these splat-quenched non-crystalline alloys at temperatures below T_g was also investigated. It was determined from these experiments that crystallization does occur when the non-crystalline alloys are aged ～ 15°C below T_g. However, the incubation time for crystalline nucleus formation was found to be substantially greater for the Cu₅₀Zr₅₀ glass. Finally, it was determined that the thermal stability of the aged glass relative to the spontaneous crystallization observed during the constant heating rate experiments above T_g decreases as a function of aging time.     

Kovacs effect in PMMA observed by low-frequency Raman scattering (boson peak)

The physical aging of the poly(methyl methacrylate) glass (PMMA) is described by its effects on the refractive index, that reflects the change of mean specific volume, and, on the other hand, on the low-frequency Raman scattering, i.e., on the boson peak. The boson peak depends mainly on the cohesion fluctuations. The memory or so-called Kovacs effect is observed by the appearance of a minimum of refractive index (i.e. a maximum of volume) as a function of the aging time at a higher temperature subsequent to an aging at lower temperature. The minimum of refractive index corresponds to a maximum of the boson peak intensity. However, the cohesion is not directly related to the volume, so that the evolution of the refractive index does not mimic exactly that of the boson peak intensity. Information on the change of cohesion by aging is obtained by enthalpy measurement. The obtained experimental results are discussed in the frame of the heterogeneous cohesion or elasticity at the nanometric scale. This clarifies the phenomenon of physical aging and the consequent Kovacs effect.     

The relation between relaxed enthalpy and volume during physical aging

Several papers have recently presented results of measurements of physical aging by studying the behavior of glassy materials quenched from temperatures above their glass transition temperature T_g. The evolution of the aging process is usually followed by plotting the relaxed enthalpy versus the accompanying decrease in volume. Here, we focus on the slope of such plots, which are found to be similar to the inverse value of the isothermal compressibility close to T_g. An explanation of this empirical result is attempted in the frame of a model that interconnects the defect Gibbs energy with properties of the bulk material.     

Glass transition and thermal expansivity in silica-polystyrene nanocomposites

The glass transition temperature T_g and the thermal expansion coefficient have been measured using the capacitive scanning dilatometry for silica-polystyrene (PS) nanocomposites with various silica volume fraction up to 50 vol.%. The glass transition temperatures for silica-PS nancomposites show a deviation from the bulk T_g together with a large scatter. Thermal expansivity decreases with increasing silica fraction both below and above T_g. A clear relaxation peak can be observed in the expansivity-temperature curve for silica-PS nanocomposites. The intensity of the peak decreases with increasing silica fraction. The decrement is larger than the value expected on the assumption that silica particles do not participate in the glass transition.     

Aging,glass transition,supercooled and equilibrium liquid states of alkali germanate glasses studied by Brillouin scattering

The elastic properties of alkali germanate glasses, xR₂O?(100 ? x)GeO₂ (R = Li, Na, K, Rb, Cs ; x = 14, 28), have been studied by Brillouin scattering in the wide temperature range up to 1200 °C. The remarkable aging effect of Brillouin shift Δν_L has been observed below a glass transition temperature T_g ≈ 500 °C. The temperature dependence of longitudinal sound velocity V_L of well annealed glasses shows the gradual decrease below T_g, while on further heating the remarkable decrease is observed above T_g. The scaled temperature dependence of V_L is nearly independent on alkali metals below the melting temperature T_m. While on further heating above T_m, the drastic decrease of V_L and increase of α_L show the remarkable alkali dependence. It may be attributed to the appearance of dynamic process related to ionic hopping of alkali metals released from glass network above T_m.     

Influence of TM and RE elements on glass formation of the ternary Al-TM-RE systems

The effects of TM and RE elements on glass formation ability (GFA) of the Al-TM-RE systems are studied systematically. The TM elements show distinct differences: critical sizes of the Al-TM-Ce systems are in the order of Ni > Co > Fe > Cu. However, the RE elements show similar effect on glass formation. These results are discussed in terms of the GFA-related factors, i.e., reduced glass transition temperature (T_rg = T_g (T_x)/T_L, where T_g, T_x and T_L are the glass transition temperature, onset crystallization temperature and liquidus temperature, respectively) and the mixing enthalpy ΔH_Al-TM. A new parameter of T_L − T_g (T_x) is potentially proposed and used to evaluate the GFA of the Al-based alloys, as well as bulk glass-formers.     

Stability of Ni-based bulk metallic glasses

Several ternary (Ni_xNb_ySn_z) refractory alloy glasses (RAGs) were studied at elevated temperatures in order to assess the stability of the amorphous state, i.e. devitrification, and to identify subsequent phase transformations in these materials. differential scanning calorimetry (DSC) experiments indicated a complex phase transformation sequence with several distinct crystallization and melting events being recorded above the glass transition temperature, T_g. Below T_g the RAG samples were studied with an in situ environmental X-ray furnace facility, which allowed step-wise isothermal ramping experiments commencing at a temperature below the reduced temperature of T/T_g ≈ 0.80. Distinct crystalline phases were observed when T/T_g ≈ 0.84 for ternary RAG alloys, while similar experiments on Zr-based Vit 106 glass alloys did not reveal any apparent phase separation until T/T_g ≈ 0.96. The phase separation kinetics followed an Arrhenius type of relationship with Ni₃Sn, and Nb₂O₅ being the principle crystalline precipitates.     

Waveguide produced by fiber on glass method using Er-doped tellurite glass

We report the fabrication of waveguides using the fiber on glass (FOG) method. Taking advantage of a Thermal Mechanical Analyzer (Shimadzu TMA-50), we were able to produce a new type of waveguide by coupling an erbium doped fiber core onto a planar glass substrate. Both optical fiber core and substrate were fabricated from tellurite glass. Important thermal characteristics of the substrate and fiber like the transition temperature T_g, the temperature for the crystallization onset T_x and the maximum crystallization temperature T_c were determined by Differential Thermal Analysis (DTA). The thermal expansion coefficient of the tellurite glass was determined by Thermal Mechanical Analysis (TMA).