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.     

Volume and enthalpy relaxation of a-Se in the glass transition region

Volume and enthalpy relaxation studies of amorphous Se have been performed in the glass transition region by mercury dilatometry and differential scanning calorimetry. For simple temperature jump experiments, as well as for more complex thermal history the volume and enthalpy relaxation data can be described by a single set of kinetic parameters for Tool-Naraynaswamy-Moynihan (TNM) model [Δh¹/R = 42.8 kK, ln(A_TNM/s) = ?133]. Slightly different non-linearity and non-exponentiality parameter were found for volume [x = 0.42, β = 0.58] and enthalpy [x = 0.52, β = 0.65] relaxation data. Similar results were obtained also for Adam-Gibbs-Scherer (AGS) model. The activation energy of viscous flow in the glass transition range is identical with the effective activation energy for relaxation process. A self-consistent data evaluation shows that at moderate departure from equilibrium, volume and enthalpy in amorphous selenium relax in the same way as expressed by TNM and AGS models. Both volume and enthalpy change can be interpreted within the same fictive temperature concept.     

The boson peak in melt-formed and damage-formed glasses: A defect signature?

We describe the preparation and characterization of a glassy form of the moderately good glassformer PbGeO₃, by mechanical damage, and compare its properties with those of the normal melt-quenched glass and the crystal. The damage-formed glass exhibits a DSC thermogram strikingly similar to that of a hyperquenched glass, implying that it forms high on the energy landscape. The final glass transition endotherm occurs within 4 K (0.006T_g) of that of the melt-quenched glass, but crystallization occurs at a lower temperature, as if pre-nucleated. In particular, we have studied the low frequency vibrational dynamics of the alternatively prepared amorphous states in the boson peak region, and find the damage-formed glass boson peak to be almost identical in shape to, but more intense than, that of the normal melt-formed glass, as previously found for hyperquenched glasses. In view of the quite different preparation procedures, this similarity would seem to eliminate equilibrium liquid clusters as a source of the boson peak vibrations, but leaves plausible a connection to force constant fluctuations or to specific vitreous state defects.     

Deceleration of surface structural relaxation in chlorine-containing silica glass due to chlorine volatilization

Both surface and bulk fictive temperatures of chlorine-containing silica glass were measured using the IR method, after thermal, mechanical and chemical treatments. A metastable equilibrium state at 1200 °C was first established for the glass by heat-treatment and a uniform fictive temperature was observed except for the sample surface created by polishing after the heat-treatment. The densified layer of the polished surface shifted the IR peak wavenumber, making the fictive temperature appear higher than the bulk. During the second heat-treatment at 950 °C, the sample with the as-heat-treated surface and uniform fictive temperature of 1200 °C developed non-uniform fictive temperature distribution with the bulk fictive temperature becoming lower than the surface fictive temperature. Usually, surface structural relaxation is faster than bulk structural relaxation and the surface fictive temperature becomes lower than the bulk fictive temperature when heat-treated at a lower temperature than the initial fictive temperature. The observed anomalous feature was attributed to chlorine volatilization from the glass surface layer creating a high viscosity surface layer. This conclusion was supported by the diffusion data of chlorine in the glass available in the literature.     

Viscosity and kinetic fragility of alkaline earth zinc phosphate glasses

Kinetic fragility indices m and F_1/2 as well as glass transition temperature T_g of alkaline earth zinc phosphate melts of molar composition 20 MO–30 ZnO–50 P₂O₅ (with M = Ba, Sr, Ca, Mg) were determined using viscometry and differential scanning calorimetry (DSC). Beam bending and concentric cylinder experiments were performed to measure the flow resistance in temperature ranges above glass transition and close to liquidus, respectively. Different upscan rates of DSC runs through the glass transition were used to correlate changes of the fictive temperature with kinetic fragility. Both methods revealed that glass transition temperature correlates negatively and kinetic fragility positively with the size of M. Metal cation mixing (M + Zn) led to a negative deviation from linearity for T_g, while exchanging M resulted in a linear dependence of T_g, if scaled with averaged charge-to-distance ratio. The fictive temperature method overestimated the compositional dependence of m by a ratio up to 1.9.     

Glass transition,thermal expansion and relaxation in B2O3 glass measured by time-resolved X-ray diffraction

In situ heating experiments using high-energy, high-intensity synchrotron radiation, can be successfully designed to study structural evolution with temperature of glassy materials. Coherent diffraction from glassy materials forms a succession of halos or diffraction maxima in reciprocal space and the variation with temperature, of the wave-vector Q_max or angular position of the first diffracted intensity I(Q_max) maximum below T_g can be used to determine the iso-structural volume expansion. In the present work we have obtained synchrotron X-ray diffraction patterns in transmission during in situ heating of a B₂O₃ glass. Samples were obtained by melting the B₂O₃ glass rods which were then air-cooled or liquid nitrogen-cooled. The evolution with temperature (and time) of the position of the first diffraction maximum of the diffraction pattern accurately reflected the thermal expansion coefficient and the relaxation behavior of the B₂O₃ glass. Such results allowed determination by diffraction of the glass transition temperature, T_g, at 580 K, as well as information on the structural relaxation during thermal annealing. The total volume changes due to relaxation were measured to be about 1.5 vol.% and 2.5 vol.%, for the air-cooled and the liquid nitrogen-cooled B₂O₃ glass, respectively.     

Simulation of surface structural relaxation kinetics in silica glass accelerated by water vapor

It is known that surface structural relaxation of silica glass takes place more rapidly than bulk structural relaxation, especially in the presence of water vapor. The effect of water vapor pressure, heat-treatment temperature and initial fictive temperature on the surface structural relaxation kinetics in silica glasses was investigated by measuring the change of the surface fictive temperature determined from the IR reflection peak shift of silica structural bands. The superimposed component of bulk structural relaxation was subtracted from the measured surface structural relaxation data to isolate the true surface structural relaxation kinetics. The obtained surface structural relaxation data as a function of fictive temperature, heating temperature and water vapor pressure were simulated with a model based on the diffusion equation with time-dependent surface concentration. The simulation model was used to predict the surface structural relaxation kinetics of the optical fiber having a high fictive temperature of ～ 1650 °C at 950 °C under 355 torr of water vapor, and it was confirmed that the present model can simulate surface structural relaxation of the fiber reasonably well.     

Electrical and dielectric properties of glass system NaPO3–KHSO4

Glass samples have been prepared in the NaPO₃–KHSO₄ binary system with the classical melting, casting and annealing steps. Electrical and dielectrical properties of glass samples were studied. Measurements of DC and AC conductivity and complex electrical permittivity of xNaPO₃–(100 ? x)KHSO₄ glass system were carried out at temperatures ranging from room temperature to temperature located 15 °C below glass transition temperature T_g. Results showed that changes of NaPO₃ concentration considerably affect values of observed parameters. DC conductivity of glass increases as NaPO₃ concentration grows until concentration x = 60. However, beyond this value a sharp decrease of DC conductivity was observed. In addition relaxation times showed abrupt changes at concentration x = 60, corresponding to the lowest relaxation times at the temperature 90 °C.     

Relaxation of polaronic charge carriers in lithium manganese spinels

Lithium manganese spinels Li_1+xMn_2−xO₄, 0 ⩽ x ⩽ 0.33, were prepared by wet chemistry technique followed by heat-treatment at 750 °C or 800 °C. Differential scanning calorimetry was used to reveal phase transitions. Electrical properties were studied by impedance spectroscopy. LiMn₂O₄ exhibited phase transition below room temperature. The transition, seen as an exothermic event in DSC and a steep decrease of conductivity upon cooling, was sharp in sample sintered at 800 °C and broadened over a range of temperature in sample sintered at 750 °C. In the low temperature phase of LiMn₂O₄, two relaxations of similar strength were observed in the frequency dependent permittivity. The low frequency process was identified as relaxation of charge carriers since the relaxation frequency followed the same temperature dependence as the dc conductivity. The high frequency process exhibited milder temperature dependence and was attributed to dipolar relaxation in the charge-ordered structure. The dipolar relaxation was barely visible in Li substituted samples, x ⩾ 0.05, which did not undergo structural phases transition. Measurements extended to liquid nitrogen temperature showed gradual lowering of the activation energy of conductivity and relaxation frequencies, behavior typical for phonon-assisted hopping of small polarons.     

Sound velocity in liquid and glassy selenium

The speed of longitudinal sound waves at 7 and 22 MHz has been measured in liquid, supercooled, and amorphous selenium, including the region around the glass transition temperature, T_g, near 35 °C. In amorphous selenium the speed of shear waves at 7 MHz was also measured. The experiments were performed with high purity Se (99.9999%) hermetically sealed in an evacuated silica ampoule. Four temperature regions with strongly different relaxation times can be distinguished between room temperature and the melting point: (1) a glassy state below T_g, which is stable on the time scale of the experiments, (2) a glassy state above T_g, which is metastable on the time scale of the experiments, (3) a region where homogeneous crystal nucleation occurs, and (4) a supercooled liquid, which is stable on the time scale of the experiments. Each region is marked by a change in the slope of the temperature dependence of the sound velocity. Near the glass transition temperature the velocities of longitudinal and transverse sound exhibit hysteresis with a step-like drop on heating and a more continuous rise on cooling. The step-like anomaly in sound velocity may be a general property of the glass transition.     

Aging of oriented polymer glasses

Dimensional (D) and enthalpy relaxation (ΔH) of oriented polymer glasses (PS and PC) have been studied as function of temperature, between T_g and T_g−20 °C, and aging time t, ranging to several weeks. The dimensional relaxation (shrinkage) and enthalpy relaxation curves verify the logarithm law D(t) ∼ H(t) ∼ log t, between an incubation τ_i and a final relaxation time τ_f. The time τ_f to reach the equilibrium (D and ΔH) follows the Vogel–Tamann–Fulcher (VFT) law. Enthalpy relaxation and shrinkage exhibit important differences. Enthalpy relaxation of oriented and isotropic polymers follows the same logarithm law, independent of the draw ratio λ and the mode of deformation, the relaxation time τ_f coincides with the relaxation time of the α segmental motions. Shrinkage depends on λ and the mode of deformation, the relaxation time τ_f is attributed to the normal mode, the relaxation time of the whole chain. Finally the shrinkages of PS and PC show some differences. PC at short aging times presents another type of dimensional relaxation which would be due to the β motions. This would be in close connection with the ductile (PC) and fragile (PS) behavior of these two polymers far below T_g.     

Investigation of the conductivity of the lithium borosilicate glass system

The lithium borosilicate system (Li₂O)_0.4(B₂O)_(0.6x)(Si₂O₄)_0.6(1−x) with x = 0, 0.2, 0.3, 0.4, 0.6, and 0.8 was investigated using impedance spectroscopy. Impedance spectra were taken in the frequency range from 50 Hz to 1 MHz and in the temperature range from 100 to 280 °C. The ac- and dc-conductivity, relaxation frequency and activation energy of the dc-conductivity were extracted from the impedance spectra. The dc-conductivity of the investigated glass samples increases almost linearly from silica rich (x = 0) to the boron rich (x = 0.8) samples. Activation energy (E_a) was found to be 0.65 eV for high conducting sample and 0.8 eV for low conducting sample, respectively. The mixed glass-former effect was not observed on the samples studied. The effect of temperature scaling of ac-conductivity was observed, which indicates, that ionic conductivity relaxation mechanism is temperature independent for samples with x = 0, 0.2, 0.3. However, some deviations from scaling were found for the samples with higher x (x = 0.4, 0.6, 0.8).     

Effect of laser irradiation on thermal and optical properties of selenium–tellurium alloy

The crystallization parameters such as glass transition temperature (T_g), onset crystallization temperature (T_c), peak crystallization temperature (T_p) and enthalpy released (ΔH_C) of the bulk Se–Te chalcogenide glass has been studied by using Differential Scanning Calorimeter (DSC), under non-isothermal condition at a heating rate of 20 K/min. The values of T_g, T_c, T_p and ΔH_C with and without laser irradiation for different exposure time have been studied. The optical absorption of pristine and laser irradiated thermally evaporated Se–Te films has been measured. The films shows indirect allowed interband transition that is influenced by the laser irradiation. The optical energy gap has been found to decrease from 1.61 to 1.38 eV with increasing irradiation time from 5 to 20 min. The results have been analyzed on the basis of laser irradiation-induced defects in the film.     

In situ high temperature 27Al NMR study of structure and dynamics in a calcium aluminosilicate glass and melt

The temperature dependence (25–1400 °C) of ²⁷Al NMR spectra and spin–lattice relaxation time constants T₁ have been studied for a calcium aluminosilicate (43.1CaO–12.5Al₂O₃–44.4SiO₂) glass and melt using an in situ high temperature probe, and the glass has been characterized by ambient temperature, high field MAS NMR. The peak positions and the line widths show a consistent behavior as motional averaging of the quadrupolar satellites increases with increasing temperature. The rate of decrease with temperature of T₁ drastically increases near the glass transition temperature T_g, which suggests a change in NMR relaxation process from vibrational to translational motions. Above the T₁ minimum (≈1200 °C), NMR correlation times obtained from T₁ are in good agreement with shear relaxation times estimated from viscosity, suggesting that microscopic nuclear spin relaxation is controlled by the same dynamics as macroscopic structural relaxation, and thus that atomic-scale motion is closely related to macroscopic viscous flow.     

Physical aging effects in selenide glasses accelerated by highly energetic γ-irradiation

Effect of ⁶⁰Co γ-irradiation on As–Se glasses stored for 20 years and subjected to saturated natural physical aging is studied using differential scanning calorimetry. It is shown that γ-irradiation activates further physical aging, which leads to an increase in glass transition temperature and endothermic peak area near glass transition region for As_xSe_100−x samples with x < 30. The observed changes are associated with additional structural relaxation of radiation-modified glass network.     

Thermodynamic characteristics of Ti-based glass-forming alloys

Based on thermodynamic characteristics of the stable metallic liquid at melting temperature and the supercooled liquid, the present work calculated the mixing enthalpy ΔH^mix, the mixing entropy ΔS^mix and the Gibbs free energy difference between the supercooled liquid and the resulting crystalline phases ΔG of typical Ti-based amorphous alloys. The results show that for the case of larger ΔS^mix, moderate ΔH^mix for the stable liquid and smaller ΔG for the supercooled liquid, Ti-based alloys tend to achieve high glass-forming ability (GFA). A new parameter, β, defined as (T_g ? T_k)/(T_l ? T_g), has been introduced to evaluate the GFA of Ti-based bulk amorphous alloys (wherein T_g, T_l, and T_k represent the glass transition temperature, the liquidus temperature, and the Kauzmann temperature, respectively). Experimental data imply that the larger the β, the better the GFA for Ti-based amorphous alloys.     

Octahedral fluoride glasses: Raman spectra and structure of niobium pentafluoride

Raman spectroscopy is used to characterize the NbF₅ phases in the temperature range 80–500 K. A new clear glass is formed by quenching the melt to liquid nitrogen temperatures having a glass transition at ～206 K and crystallization at ～233 K. For all phases including the melt, the glass, the supercooled liquid, the crystalline solid and the gas, the Raman spectra show a rather common high frequency band at ～760 cm^?1 which is attributed to the Nb–F terminal frequency of partially bridged ‘NbF₆’ octahedra. Based on the systematics of the Raman spectra for all phases and the literature physicochemical data a model is proposed for the glass and the liquid phases where ‘NbF₆’ octahedral bridged in cis and/or trans configurations form a variety of cyclic and/or chain structures which intermix building up the overall structure. At exceptionally low energies (<11 cm^?1) a rather weak in intensity Boson peak is observed in the glass which shifts to even lower energies with increasing temperature. Librational and/or tortional motions of the bridged octahedra participating in the glass structure are possible candidates for the origin of this peak.     

Effects of hydration,annealing, and melting on heat transport properties of fused quartz and fused silica from laser-flash analysis

Thermal diffusivity (D) at high temperature (T) was measured from 15 samples of commercial SiO₂ glasses (types I, II, and III with varying hydroxyl contents) using laser-flash analysis (LFA) to isolate vibrational transport, in order to determine effects of impurities, annealing, and melting. As T increases, D_glass decreases, approaching a constant (~ 0.69 mm²s^? 1) above ~ 700 K. From ~ 1000 K to the glass transition, the slope of D is small but variable. Increases of D with T of up to 6% correlate with either low water and/or low fictive temperature and are attributed to removal of strain and defects during annealing. Upon crossing the glass transition, D substantially decreases to 0.46 mm²s^? 1 for the anhydrous melt. Hydration decreases D_glass, makes the glass transition occur over wider temperature intervals and at lower T, and promotes nucleation of cristobalite from supercooled melt. Due to the importance of thermal history, a spread in D of about 5% occurs for any given chemical type. Combining prior steady-state, cryogenic data with our average results on type I glass provides thermal conductivity (k_lat = ρC_PD) for type I: k_lat increases from ~ 0 K, becoming nearly constant above 1500 K, and drops by ~ 30% at T_g. We find that D^? 1(T) correlates with thermal expansivity times temperature from ~ 0 K to melting due to both properties arising from anharmonicity.     

Fictive temperature distribution in highly Ge-doped multimode optical fibers

In this study, FTIR FPA (focal plan array) detector was used to image the ‘bond-stretching’ vibration mode observed near σ = 1120 cm⁻¹ of highly Ge-doped graded index multimode optical fibers (GI-MMF). Next, as calibration curves between σ and the fictive temperature T_f are not available in the literature for highly Ge-doped glasses (above 7 wt%), we have determined our own calibration curves from 1 to 30 wt% in Ge. Then, we have applied these corrections to our σ measurements in GI-MMF in order to estimate, for the first time to our knowledge, the fictive temperature distribution within MMF cross-section.