Dynamics of structural relaxation in bioactive 45S5 glass.

Kinetics of physical aging in archetypic 45S5 bioactive silicate glass composition with different types of phase separation are studied in situ below the glass transition temperature (T g). The qualitative nature of aging is found to be almost independent of the structural differences on the micrometer scale. A well-expressed step-like behavior in the enthalpy recovery kinetics is observed for aging temperatures T a ∼ 0.90T g and T a ∼ 0.85T g, which, however, disappears when the aging occurs at T a ∼ 0.95T g. The overall kinetics are described by a stretched-exponential function with stretching exponent close to 3/7 at T a ∼ 0.95T g, and 1/3 when the aging temperature drops to ∼0.90T g and below. The values correlate well with the predictions of Phillips' diffusion-to-traps and percolating fractals models. Appearance of step-like behavior at larger departure from T g is attributed to the hierarchical scheme of approaching equilibrium based on an alignment-shrinkage mechanism of physical aging proposed earlier for chalcogenide glasses.

Giant visible and infrared light attenuation effect in nanostructured narrow-bandgap glasses.

A unique effect of Bi on the optical and electrical properties of mixed Ga-containing Ge-Se and Ge-Te glasses is discovered. It is shown that glass with a low Bi content is completely transparent in a 3-16 µm spectral range, while the glass with a slightly higher Bi content possesses a large (>10 db/mm) attenuation coefficient, making a ∼millimeter thick glass sample fully opaque to VIS-IR radiation. Despite this contrast, both types of glass are found to retain their semiconducting properties, the DC conductivity at room temperature, σDC∼10-3 S/m, being comparable to that of silicon.

Crossover between cooperative and fractal relaxation in complex glass-formers.

Kinetics of physical aging at different temperatures is studied in situ in arsenic selenide glasses using high-precision differential scanning calorimetry technique. A well-expressed step-like behaviour in the enthalpy recovery kinetics is recorded for low aging temperatures. These fine features disappear when the aging temperature (T a) approaches the glass transition temperature (T g). The overall kinetics is described by stretched exponential function with stretching exponent close to 3/5 at T a > ~0.95 T g almost independent on glass composition, and 3/7 when the aging temperature drops to ~0.9 T g. These values are consistent with the prediction of Phillips' diffusion-to-traps model. Further decrease in aging temperature to ~0.85 T g leads to the appearance of step-like behaviour and stretching exponent of 1/3 for the overall kinetics, which is the limiting value predicted by random walk on the fractal model. Such behavior is explained as crossover from homogeneous cooperative relaxation of non-percolating structural units to high-dimensional fractal relaxation within hierarchically-arranged two-stage physical aging model.

Study of Ga incorporation in glassy arsenic selenides by high-resolution XPS and EXAFS.

Effect of Ga addition on the structure of vitreous As2Se3 is studied using high-resolution X-ray photoelectron spectroscopy and extended X-ray absorption fine structure techniques. The "8-N" rule is shown to be violated for Ga atoms and, possibly, for certain number of As atoms. On the contrary, Se keeps its 2-fold coordination according to "8-N" rule in the amorphous phase throughout all the compositions. Crystalline inclusions appear in the amorphous structure of the investigated glasses at Ga concentrations greater than 3 at. %. These inclusions are presumably associated with Ga2Se3 crystallites and transition phases/defects formed at the boundaries of these crystallites and host amorphous matrix. The existence of Ga-As and Se-Se bonds in the samples with higher Ga content is supported by present studies.

Influence of phase separation on the devitrification of 45S5 bioglass.

The devitrification of the 45S5 variety of bioactive glasses (BGs) in relation to phase separation is studied with scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry and positron annihilation lifetime spectroscopy techniques. It is shown that the type of phase separation (such as spinodal vs. droplet-like) has a pronounced effect on the activation energy of viscous flow and crystallization, the onset temperature of crystallization and the void size distribution at the nanoscale. Generally, the Johnson-Mehl-Avrami (JMA) relation does not describe crystallization kinetics in bulk 45S5 BG. However, for powder samples (<300 µm) the difference in crystallization kinetics, which is surface-driven for the two kinds of glasses, becomes much smaller, and can be described with the JMA relation under some circumstances.

Complex structural rearrangements in As-Se glasses.

Structural relaxation of As-Se glasses through the glass-to-supercooled liquid transition interval is studied with temperature-modulated differential scanning calorimetry. It is shown that connectivity of glass network and long-term physical ageing change not only the full width at half maximum of the out-of-phase component of complex heat capacity, which is conventionally used for analysis, but also its asymmetry value. The latter is shown to carry very important information on the dynamic heterogeneity in glasses. Raman spectroscopy is used as complementary technique to reveal possible structural rearrangements in the investigated glass network.

Structural evolution of Ga-Ge-Te glasses by combined EXAFS and XPS analysis.

The structural evolution of GaxGeyTe100-x-y glasses in the vicinity of GeTe4-GaTe3 pseudo-binary tie-line is determined with high-resolution X-ray photoelectron (XPS) and extended X-ray absorption fine structure (EXAFS) spectroscopies. The analysis of XPS data is complicated by similar electronegativity values for the constituent chemical elements, but then the interpretation is facilitated by information from complementary EXAFS analysis of the structure around each element independently. The results show 4∕4∕2 coordination for Ga∕Ge∕Te atoms and absence of Ga(Ge)-Ge(Ga) bonds or extended Te clusters in significant concentrations within the whole range of studied composition. The observed structural features correlate well with the measured basic physical properties of Ga-containing germanium telluride glasses.

Step-wise kinetics of natural physical ageing in arsenic selenide glasses.

The long-term kinetics of physical ageing at ambient temperature is studied in Se-rich As-Se glasses using the conventional differential scanning calorimetry technique. It is analysed through the changes in the structural relaxation parameters occurring during the glass-to-supercooled liquid transition in the heating mode. Along with the time dependences of the glass transition temperature (T(g)) and partial area (A) under the endothermic relaxation peak, the enthalpy losses (ΔH) and calculated fictive temperature (T(F)) are analysed as key parameters, characterizing the kinetics of physical ageing. The latter is shown to have step-wise character, revealing some kinds of subsequent plateaus and steep regions. A phenomenological description of physical ageing in the investigated glasses is proposed on the basis of an alignment-shrinkage mechanism and first-order kinetic equations.

Cooperative rearranging region size and free volume in As-Se glasses.

Glasses of the As-Se system have been used as model objects of the covalent disordered inorganic polymers to investigate the correlation between the cooperative rearranging region (CRR) size determined at the glass transition temperature and the free volume fraction in the glassy state. The CRR size has been determined using temperature modulated differential scanning calorimetry data according to Donth's approach, while the free volume fraction in the investigated materials has been estimated using positron annihilation lifetime spectroscopy data. The obtained results testify that the appearance of open-volume defects greater than 80 Å(3) leads to a significant decrease in the CRR size.