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.
Methodological possibilities of positron annihilation lifetime (PAL) spectroscopy applied to characterize different types of nanomaterials treated within three-term fitting procedure are critically reconsidered. In contrast to conventional three-term analysis based on admixed positron- and positronium-trapping modes, the process of nanostructurization is considered as substitutional positron-positronium trapping within the same host matrix. Developed formalism allows estimate interfacial void volumes responsible for positron trapping and characteristic bulk positron lifetimes in nanoparticle-affected inhomogeneous media. This algorithm was well justified at the example of thermally induced nanostructurization occurring in 80GeSe2-20Ga2Se3 glass.
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.
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