MASTER CURVE APPROACH TO POLYMER CRYSTALLIZATION KINETICS

Nonisothermal crystallization kinetic data obtained from differential scanning calorimetry (DSC) for a poly(ethylene terephthalate) are corrected for the effects of temperature lag between the DSC sample and furnace using the method of Eder and Janeschitz-Kriegl which is based on experimental data alone without resort to any kinetic model. A method is presented for shifting the corrected nonisothermal crystallization kinetic data with respect to an arbitrarily chosen reference temperature to obtain a master curve. The method is based on experimental data alone without reference to any specific form of kinetic model. When the isothermal crystallization kinetic data for the same material are shifted with respect to the same reference temperature, a master curve is also obtained which overlaps to a large extent the corresponding master curve from nonisothermal data. It follows that nonisothermal DSC measurements provide the same crystallization kinetic information as isothermal DSC measurements, only over a wider range of temperatures. The shift factors obtained from experimental data alone are compared in turn with the corresponding values calculated from the Avrami equation, the Hoffman-Lauritzen expression, and the Nakamura equation as a means of evaluating these models individually. It is concluded that the Avrami equation is very good at describing isothermal crystallization kinetics, the Hoffman-Lauritzen extrapolation of the limited isothermal data to a wide range of temperatures is quite good, and the Nakamura equation yields reliable crystallization kinetic information over a narrower range of temperatures than nonisothermal data alone without using any specific model.