ABSTRACT
Mathematical models of degradation-relaxation kinetics are considered for jammed thick-film systems composed of screen-printed spinel Cu0.1Ni0.1Co1.6Mn1.2O4 and conductive Ag or Ag-Pd alloys. Structurally intrinsic nanoinhomogeneous ceramics due to Ag and Ag-Pd diffusing agents embedded in a spinel phase environment are shown to define governing kinetics of thermally induced degradation under 170 °C obeying an obvious non-exponential behavior in a negative relative resistance drift. The characteristic stretched-to-compressed exponential crossover is detected for degradation-relaxation kinetics in thick-film systems with conductive contacts made of Ag-Pd and Ag alloys. Under essential migration of a conductive phase, Ag penetrates thick-film spinel ceramics via a considerable two-step diffusing process.
ABSTRACT
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.
ABSTRACT
The theory of strange attractors is shown to be adequately applicable for analyzing the kinetics of light-assisted physical aging revealed in structural relaxation of Se-rich As-Se glasses below glass transition. Kinetics of enthalpy losses is used to determine the phase space reconstruction parameters. Observed chaotic behaviour (involving chaos and fractal consideration such as detrended fluctuation analysis, attractor identification using phase space representation, delay coordinates, mutual information, false nearest neighbours, etc.) reconstructed via the TISEAN program package is treated within a microstructure model describing multistage aging behaviour in arsenoselenide glasses. This simulation testifies that photoexposure acts as an initiating factor only at the beginning stage of physical aging, thus facilitating further atomic shrinkage of a glassy backbone.
ABSTRACT
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.
