The Ozawa’s generalized time concept and YZ-master plots as a convenient tool for kinetic analysis of complex processes

Journal of Thermal Analysis and Calorimetry, 113 (2013) 1437-1446

The concept of generalized time θ=∫exp(−Ea/RT)dt θ = ∫ exp ( − E a / RT ) d t in non-isothermal kinetics was introduced by Ozawa in 1965, together with the well-known isoconversional plot, i.e., Ozawa plot. The generalized time is the key concept to tie the kinetic data under varying temperature to the kinetic relationship at a constant temperature. It is well known that many processes studied by thermal analysis and calorimetry reveal a complex nature. Therefore, the generalized time concept seems to be very useful for the description of the change in the rate behavior depending on the fractional conversion. Using the concept of θ, three kinds of experimental master plots can be formalized in differential, integral, and multiplied forms. Among others, combination of the differential and multiplied master plots, y(α) = (dα/dθ) and z(α) = (dα/dθ)θ, show a high performance to discriminate the kinetic model based on the maxima condition of y(α y*) and z(α z*). The α y* − α y* kinetic plot is a useful tool to visualize the complexity of the kinetic process and to determine the most suitable kinetic model. The usefulness of α y* − α y* kinetic plot and the YZ-master plots is illustrated as exemplified by the kinetic analyses of complex crystallization processes of the as-prepared, thermally and mechanically treated amorphous zirconia.

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