Differential scanning calorimetry was used to investigate the isothermal crystallization, subsequent melting behavior, and nonisothermal crystallization of syndiotactic 1,2-polybutadiene (st-1,2-PB) produced with an iron-based catalyst system. The isothermal crystallization of two fractions was analyzed according to the Avrami equation. The morphology of the crystallite was observed with polarized optical microscopy. Double melting peaks were observed for the samples isothermally crystallized at 125-155 degreesC. The low-temperature melting peak, which appeared approximately 5 degreesC above the crystallization temperature, was attributed to the melting of imperfect crystals formed by the less stereoregular fraction. The high-temperature melting peak was associated with the melting of perfect crystals formed by the stereoregular fraction. With the Hoffman-Weeks approach, the value of the equilibrium melting temperature was derived. During the nonisothermal crystallization, the Ozawa method was limited in obtaining the kinetic parameters of st-1,2-PB. A new method that combined the Ozawa method and the Avrami method was employed to analyze the nonisothermal crystallization of st-1,2-PB. The activation energies of crystallization under nonisothermal conditions were calculated. (C) 2005 Wiley Periodicals, Inc.