A three-phase model, comprising mobile amorphous fraction (MAF), rigid amorphous fraction (RAF) and crystalline fraction (C), has been applied to interpret the thermal transitions and structure of cold-crystallized isotactic polystyrene (iPS) from below the glass transition temperature, T-g, to above the melting point. Quenched amorphous iPS films were isothermally crystallized at different temperatures for 12 h. The fraction of crystalline phase, phi(c), was measured by differential scanning calorimetry (DSC), wide angle X-ray scattering and Fourier Transform infrared spectroscopy. The fraction of the mobile amorphous phase, phi(MAF), was obtained from the heat capacity increment at the glass transition temperature. In the three-phase model, the fraction of the rigid amorphous phase, phi(RAF), was found from 1 - phi(MAF) - phi(c).Specific heat capacity measurements by standard DSC confirm that the experimental baseline heat capacity conforms to a three-phase model for temperatures ranging from below T-g, up to the relaxation of RAF. The relaxation of RAF appears as a sigmoidal change in heat capacity accompanied by excess enthalpy, in which solid-like RAF is converted to an identical amount of liquid-like MAF. At temperatures above the relaxation of RAF, either one or two major crystal melting endotherms are observed in standard DSC, dependent upon crystallization temperature. However, using quasi-isothennal temperature modulated DSC, we always observed two reversing melting endotherms. The effects of annealing on iPS structure during the quasi-isothermal measurement were assessed using small angle X-ray scattering (SAXS). Combining the DSC and SAXS results, a model for the melting of iPS lamellae at low heating rates is presented. C) 2005 Elsevier Ltd. All rights reserved.