Jeziorny Method Should Be Avoided in Avrami Analysis of Nonisothermal Crystallization

The Jeziorny method treats nonisothermal crystallization data by replacing the variable temperature (T) values with the corresponding values of time and substituting them into the isothermal Avrami plot, ln[−ln(1 − α)] vs. lnt. For isothermal data, the slope of this plot is the Avrami exponent, n and the intercept is the rate constant, kA. This does not hold for nonisothermal data. Theoretical analysis suggests that in the case of nonisothermal data the intercept cannot be interpreted as kA, and its “correction” by dividing over the temperature change rate β is devoid of any meaning. In turn, the slope cannot be interpreted as n. It is demonstrated that the slope changes with time and its value depends not only on n but also on the temperature, temperature range, and activation energy of crystallization. Generally, the value of the slope is likely to markedly exceed the n value. The theoretical results are confirmed by analysis of simulated data. Overall, the Jeziorny method as well as other techniques that substitute nonisothermal data into the isothermal Avrami plot should be avoided as invalid and useless for any reasonable Avrami analysis. It is noted that n can be estimated from the nonlinear plot of ln[−ln(1 − α)] vs. T.